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^ Historical Development of Models of the Components and Structure of the Atom
Also the model of the atom has changed by time
Wavelength, Frequency, and Energy of Light
Electromagnetic radiations are considered as waves and those are defined by wavelength(λ) which is the
distance between two repeating points, and frequency(v) which is the number of waves in each seconds.
Also the equation shown below which is the formula for speed of Light shows that the wavelength and
Frequency are inversely related. Therefore, in Vacuumed condition, the speed of light us 3.0 x 10^8 meters
per second.
(Wavelength)(Frequency) = Speed of Light
(λ)(v)=c
Max Planck found that the energy of electromagnetic waves is proportional to the frequency and inversely
proportional to the wavelength.
Hv = E = h(c/λ)
The Bohr Model of the Atom
Neil Bohr brought up the solar system model which was the idea that Only certain special orbits known as
discrete orbits for electrons are allowed inside an atom, and While revolving in discrete orbits the electrons do
not radiate energy. Also the discrete orbits are called energy levels. These orbitals or shells are represented
by the letters K, L, M, N… or the numbers, n = 1, 2, 3, 4
The Size of an Atom
The momentum of the electron is related to the size of the electron’s orbit, and it is expressed as :
Mv = (nh)/(2rπ )
Using this equation the Bohr radius which is 53pm, gives theoretical size of a hydrogen atom.
The Structure of the Atom
Principal energy levels(shells) are orbits followed by electrons around an atom's nucleus, and the first four
energy levels can hold 2,8,18,32 electrons. Also each principal energy levels within an atom contains more
sublevels(subshells). In subshells, all expect the first have p sublevels, then d and f sublevels are found in
more than one principal energy levels. Orbital is defined as region of space the has a high electron density
and orbitals are contained in each sublevels.
Sample questions
1. Our inability to know precisely the position and momentum of a subatomic particle is summarized by
(a) Rydberg equation
(b) Heisenberg uncertainty principle
(c) Hund's rule
(d) Pauli exclusion principle
(e)
2. Which of these symbols represents an orbital?
(a) n and s
(b) s and f
(c) n, s, and f
(d) ml and ms
3. Which was used to determine the charge of the electron?
(a) The gold foil experiment
(b) Deflection of cathode rays by electric and magnetic fields
(c) The oil drop experiment
(d) The mass spectrometer
4. Which of the following principles is NOT part of Dalton's atomic theory?
(a) Chemical reactions are simple rearrangements of atoms.
(b) Atoms follow the law of multiple proportions.
(c) Each atom of an element is identical to every other atom of that element.
(d) All matter is composed of atoms.
5. The valence electrons are
(a) all electrons in an atom beyond the preceding noble gas
(b) all outermost electrons in a sublevel
(c) sand any p electrons in the highest energy level or shell
(d) electrons in the last unfilled sublevel
6. Which equation best expresses the energy of a photon?
(a) E = ½(mv^2)
(b) E = mc^2
(c) E = IR
(d) E = hv
7. Which of the following elements has the greatest number of p electrons
(a) As
(b) Si
(c) Fe
(d) Cl
8. Which quantum number describes the spin of an electron?
(a) n
(b) l
(c) ml
(d) ms
9. Which of the following atoms has the most unpaired electrons?
(a) Mg
(b) Ti
(c) Al
(d) Fe
Answers and Explanations
1. (b) The Heisenberg uncertainty principle says that the more precisely we know the position, the less
precisely we know its momentum, and vice versa.
2. (b) The s and f are symbols used for orbitals, while the other symbols represent quantum numbers.
3. (c) The Millikan oil-drop experiment determined the charge of the electron independent of the mass.
4. (b) The law of multiple proportions is a consequence of the atomic theory
5. (c) Valence electrons are the electrons in the outermost energy level of the atom. Only the s and p
electrons are in the same energy level as the period in the periodic table.
6. (d) E = hv is the equation for determining the energy of a photon.
7. (a) Arsenic has a total of 15 p electrons
8. (d) The ms quantum indicates the spin of an electron.
9. (d) Iron has an electron configuration of IFel 4s^2 3d^6, giving it four unpaired electrons
Chapter 2 : The Periodic Table
What is the Periodic Table
The periodic table is a systematic organization of the elements, and the elements are arranged in order of
atomic number. the atomic number is at the top of a box in the periodic table and the atomic weight of an
element is on the bottom. The rows are called periods and the columns are called groups. The elements in
the same group have similar property.
There are five groups in periodic table :
Metals are on the left side of the periodic table. Some properties of metals include shiny luster, conducting
heat and electricity, solidity (except mercury). Nonmetals are on the right side of the periodic table (with
the exception of H). Elements on the steplike line are metalloids (except Al, Po, and At). Their properties
are sometimes like metals and sometimes like nonmetals.
Electrons, Protons, and Neutrons
By reading the periodic table, the number of electrons, protons and neutrons could be easily found that :
Protons = atomic number
Electrons = atomic number
Electrons in ion = atomic number - charge of the ion
Neutrons = isotope mass - atomic number
Ions
When an atom of a group of atoms loses or gains electrons, it becomes an ion. Cations are formed when at
least one electron is lost. Monatomic cations are formed by metals. Anions are formed when at least one
electron is gained.
The chart below are common cations and anions.
Atomic Mass
Weighted average of isotopes could be expressed as :
Weighted average = the sum of (the mass of isotope i)(abundance of isotope i)
Today we can determine the masses of individual atoms with a high degree of accuracy., and it is convenient
to use the atomic mass unit when dealing with these extremely small masses:
1 amu = 1.66054 * 10^(-24)g
1 g = 6.02214 * 10^(23) amu
Also, most elements occur in nature as mixtures of isotopes. We can determine the average atomic mass of an
element, usually called the element’s atomic weight, by summing the masses of its isotopes multiplied by
their relative abundances:
Atomic weight = (isotope mass) * (fractional isotope abundance) / all isotope of the element
Sample questions
1. Trends in the periodic table show that elements become more metallic in character from the top of a
group to the bottom. Which of these is an element whose properties are opposite those of the element at
the top of its group?
a) Krypton
b) Strontium
c) Uranium
d) Bismuth
2. The halogen in this group is
a) Bismuth
b) Strontium
c) Uranium
d) Bromine
3. The element that contains 38 protons is
a) Krypton
b) Strontium
c) Uranium
d) Bromine
4. The number of electrons, protons, and neutrons in argon-40 is
a) 18 e, 18 p, 40 n
b) 40 e, 40 p, 18 n
c) 18 e, 22 p, 18 n
d) 18 e, 18 p, 22 n
5. How many protons, neutrons, electrons are in an atom of bromine?
a) 35 p, 45 n, 35 e
b) 45 p, 35 n, 45 e
c) 80 p, 35 n, 80 e
d) Neutrons cannot be determined unless an isotope is specified
6. Chemical properties of elements are defined by the
a) electrons
b) ionization energy
c) protons
d) electronegativity
7. silver has two naturally occurring isotopes. 10 Ag has a mass of 106.91 amu and accounts for 51.85% of
silver atoms. If the atomic mass of silver is 107.87 amu, what the mass of an atom of the second silver
isotope?
a) 108.0 amu
b) 107.4 amu
c) 108.9 amu
d) 106.6 amu
8. In which pair of elements is the larger atom listed first?
a) K, Ca
b) Na, K
c) Cl, S
d) Mg, Na 20.
9. Which of the following elements has the most negative electron affinity?
a) Rb
b) F
c) S
d) Al
10. In general, atomic radii decrease from left to right across a period.The main reason for this behavior is
a) the number of neutrons in the nucleus increases
b) the number of electrons increases
c) the atomic mass increases
d) the effective nuclear charge increases
Answers and Explanations
1. (D) Bismuth is a metal, and nitrogen is a nonmetal.
2. (D) Bromine is a halogen.
3. (B) Strontium has 38 protons.
4. (D) Both the number of electrons and the number of protons are equal to the atomic number of Ar, 18,
The number of neutrons is the difference between the atomic mass and the atomic number (40 - 18 = 22)
5. (D) we can determine the number of neutrons only if a specific isotope is selected.
6. (A) Electrons are the first parts of the atoms to encounter each other in a collision between atoms.
7. (C) Since 51.85% of the silver atoms have a mass of 106.91 amu, the other isotope must contribute to
48.15% of the total mass. Let x stand for the mass of the other isotope. The problem can be set up as
(0.5185) (106.91 amu) + (0.4815)x = 107.87 amu
x = 108.9 amu
8. (A) In a period, the largest atom is closest to the left side of the periodic table. In a group, the atoms
increase in size from top to bottom. Therefore Kis a larger atom than
9. (B) The more negative the electron affinity value, the more likely the atom will accept an electron in the
gaseous state. The general trend is that electron becomes more negative from left to right across a period
and also from bottom to top Its position in the periodic table suggests that the atom with the most negative
electron affinity is fluorine.
10. (D) The effective (unshielded core electrons) nuclear charge increases, contracting by a shell of e^-
Chapter 4: Ionic Compounds, Formulas, and Reactions
A chemical formula is an easier method to describe compounds. It shows the number of atoms of each
element in a compound. Atomic symbols from the periodic table are used for identify the elements in a
compound. A subscript is used to show amount of atom when there are more than one atom of an element
in the formula
To clarify and to provide additional information, use parentheses in chemical formulas. To distinguish
different atoms part of a molecule.
C a(OH)2
Hydrates are compounds that contains water. C a(OH)2 is an example of a hydrate. These compounds
have a fixed number of water molecules called the water hydration, in their crystal lattices. It is written after
a ot that is placed in the middles of the line to show the water of hydration clearly in the chemical formula.
Common prefixes for hydrates are listed below:
Number Prefix
1 mono-
2 di-
3 tri-
4 tetra-
5 penta-
6 hexa-
7 hepta-
8 octa-
9 nona-
10 deca-
The compounds in the list above are ionic and those states the simple ratio of the atoms in a crystal of the
substance. This is called empirical formula.
Molecular formulas are used for the compounds that have covalent bonds. Molecular formulas are not
empirical formulas. They state real numbers of each atom present in a single molecule.
Structural formula is another type of molecular formula. It shows a way the atoms are connected with each
other and the covalent bond.
Example of structural formula
Chemical Reactions and Equations
Every chemical reactions are originally same. A chemical equation has consists of two parts: reactants and
products. Reactants are substances that take part in the reaction and undergo change. Products are the
substances formed after the reactants are consumed.
Reactants are placed on the left side and the products on the right side. Arrows states the converting of the
reactants to products
The chemical equation shows the process of the reaction.
Balancing a Chemical Equation
Since Chemical equation must be balanced, both side of the arrow must contain same number of each
atom. Law of conservation of matter is satisfied when the Chemical equation is balanced.
By placing the appropriate coefficients in front of the formulas of the reactant, equations are balanced.
One of the common reaction types is Combustion reaction. A combustion reaction is where a substance
reacts with oxygen and releases a lot of energy. In this reaction, there is always oxygen on the reactant side
and carbon dioxide and water on the product side.
Two methods to determine the coefficients are Inspection method and Ion-electron method.
Inspection method is counting the number of each atom in the equation on the reactant side and then on
the product side and balancing the equation by adding coefficients where needed. This requires a lot of
effort because even a small mistake can ruin everything.
Ion-electron method is used for balancing oxidation-reduction reactions which we will learn in later
chapters.
Reaction types
By comparing the properties by classifying chemical reaction, we can distinguish the groups of chemical
reactions.
Double-Replacement Reactions
Two compounds react and Cation in the first compound goes to the second compound and vice versa.
Neutralization reactions
- When one reactant is an acid and the other is base, it is neutralization reactions
which is special type of double replacement reaction.
For examples - acid + base → H2O + Salt
H^+Cl + NaOH^- → H2O + Nacl
Synthesis reactions
- Two or more elements to form a compound in reactants.
For examples - 2mg(s) + O2(g) → 2MgO(s)
Formation Reactions
- Except the product must have a coefficient of 1, it is the same as a synthesis reaction. The reactants
are the elements in their normal state at room temperature and atmospheric pressure. The use of
fractional coefficients for the reactants is permitted in a formation if it is important.
Addition Reactions
- Simple molecule or an element is added to another molecule in these reactions
Decomposition Reactions
- When a large molecule decomposes into its elements or into smaller molecules, these reactions
occur.
Net Ionic Equations
- Only one compound reacts when ionic compounds react in AQ. Spectator ions do not react and this
is other ions. Equation into ionic form focuses on real reaction and to find substitute reactants to
achieve the same result.
Half Reaction Equations
- These reactions are used with oxidation-reduction reactions and in describing electrochemical
processes. If electrons are on the reactant side and an oxidation reaction if electrons are products,
the half reaction is reduction reaction.
Bonding
Chemical formed when elements combine with each other. Bonds help predict many physical and chemical
properties of molecules and compounds such as reactivity, shape, solubility, physical state, and polarity.
When two atoms share valence electrons, this is called covalent bond. When one atom loses one and other
gains one, it is called ionic bond.
Chemical Driving forces
There are three fundamental principles to build an possibility for a reaction in double replacement reaction.
These three are the Driving forces
- The water’s formation is the strongest in driving force. Where the water is a product, the
double replacement reaction occurs
- Formation of a precipitate is another indicator of a strong driving force
- Nonionic formation from ionic reactants is another driving force.
Sample questions
1. Which of these carries a single negative change?
a. Ammonium ion
b. Calcium ion
c. Bromide ion
d. Hydroid ion
2. The correct name of the SrBr2 is B
a. Stone bromide
b. Strontium bromide
c. Steam bromide
d. Strontium brokide
3. Find the two atoms will form isoelectronic ions?
a. Cl and f
b. Na and B
c. H and Na
d. Na and F
4. What atom match to the electronic configuration 1s^2 2s^2 2p^6 3s^2 ?
a. Na
b. Al
c. Mg
d. K
5. Find the solubility of potassium nitrate
6. Balanced equation for the reaction of AQ solutions of potassium sulfide and hydrochloric acid
7. The substances listed on the left side of a chemical reactions are the
a. Product
b. Coefficients
c. Precipitates
d. Reactants
8. Mg3(P04)2 + H2 → Mg + H3Po4
a. Decomposition
b. Single replacement
c. Synthesis
d. Double replacement
Answers
1. C, this is because bromium is in the 7th group, one step away from the octet. And because of that, it will
gain an electron and became a single negative anion
2. B, for covalent compounds, we simply name them individually sequentially step by step.
3. A, those are in the same group, and thus have the same amount of valence electrons
4. C, we can count the number of electrons and compare them with the respective atoms
5. The solubility of sodium nitrite is quite high because nitrite has a high solubility probability
6.
7. d), The species that are on the left of the reaction are called reactants
8. B, this is a single replacement reaction because PO4 moves from one compound to the other
Chapter 5 : Covalent Compounds, Formulas, and Structure
A covalent bond, also known as a molecular bond, results from the sharing of electrons by a pair of
atoms. It represents another way of which elements may combine to form compounds and at the same time
attain noble gas electronic configuration. When ionic bonding is electrical attraction of oppositely charged
ions, in covalent compounds and atoms are attached to each other. Molecules are the groups of atoms that
compose the compound with covalently bonded. Lewis electron-dot structures are the easier way to show
this sharing of electrons. In this structures, S and P electrons are shown as dots that are arranged the atomic
symbol.
In this diagram, the S and P electrons are shown as dots arranged around the atomic symbol.
What represents Covalent Bond is the donation electron of Atoms when they share electrons between two
atoms. One atom donates one electron and second donates one too.
Double bond exists when two pairs of electrons are shared between two atoms.
Triple bond exists when two atom share three pairs of electrons
If the Lewis structure shows eight electrons around each atom, the Octet rule says that the noble - gas
configuration will be achieved.
Lewis structures of the diatomic elements is that states the electrons of one atom are represented as
dots.
Lewis structures of the diatomic elements
LEWIS STRUCTURE OF MOLECULES
The first important thing to do for larger molecule is to determine the general arrangement of the atoms,
Skeleton. There are some rule to determine Skeleton
1. Put carbon atom to start the skeleton in compounds with more than one carbon atom.
2. Since carbon only form one covalent bond, it is never in the central atom
3. Halogen is not be in the central atom because it only forms one covalent bond
4. Oxygen is rarely a central atom. It only have two covalent bond
5. The atom that appears only once in the formula will be the central atom
After determine skeleton, you need to follow this steps
1. All atoms’ valence electrons are added together
2. Must take into account the electrons used to form the ion if the substance is a polyatomic ion.
3. Must make bonding pairs
4. If there are remaining electrons, use it for octets. These are nonbonding pairs
5. After all, if there are still remaining electrons, they are added to central atom
The most common electron - deficient molecules involve boron
To count the electrons around each atom, drawing a circle that includes all nonbonding electrons and all
bonding electrons for that atom
The central atom can have 12 electrons as maximum
Multiple Covalent Bonds
There are 18 valence electrons in Sulfur dioxide So2
Two probable equally in structure are called resonance structure
Formal charges
To verify the structures, find the experiment evidence to know Lewis structure is reasonable.
Calculating Formal Charge is the another way to see reliability of Lewis structure
To calculate the formal charge, assign the atoms that are proposed in Lewis structure to a specific atom
Steps for calculate formal charge:
- Count electrons that are not used for bonding by the atom
- Count half of the atom’s bonding electrons
- Add two steps above
- Valence electrons minus assigned electrons and you get the formal charge
The equation is :
Valence equations - (lone pair of elections + (½ bound electrons))
Resonance Structures
Resonance Structures are molecules that have the same molecular composition but have different placement
of double bonds.
Example of Resonance structures
Covalent Bond Polarity and Electronegativity
If the bond between the atom is polar it means there is an unequal sharing of electrons between two
molecules. Or, two molecules have different electronegativities.
Electronegativity is the ability of an atom to attract a pair of electrons to itself. Each element on the
periodic table is assigned an electronegativity value. The higher the value, the stronger ability to attract
electrons. A bond of an electronegativity difference more than 0.5 is considered polar
One of the important diagonal trends in the periodic table is that the electronegativity increases lower left
corner to upper right corner in the periodic table.
- Showing electronegativity in the periodic table.
Important concepts
Octet rule and when it can be disobeyed
- Molecules with an odd number of electrons
- Molecules in which an atom has less than an octet
- Molecules in which an atom has more than an octet
Bond Polarity
- Bond polarity depends on the electronegative difference between the two atoms which form bond
Electronegativity
- Property of an atom which increases with its tendency to attract the electrons of a bond.
Dipole Moment
- When two electrical charge, of opposite sign and equal magnitude are separated by a distance and
electric dipole is established.
Practice Questions
1. Pi bonds are formed by
a. Side to side overlap of s orbitals
b. End to end overlap s orbitals
c. Side to side overlap of p orbitals
d. End to end overlap of p orbitals
2. How many pi bonds are there in a double bond ?
3. How many pi bond are there in a single bond?
4. How many sigma bonds are there in a triple bond?
5. How many electrons should oxygen have around its lewis dot model?
6 ~10. Write all the resonance structure for the followings molecule
Chapter 6: Stoichiometry
Stoichiometry is the area of study that examines the quantities of substances consumed and produced in
chemical reactions.
Stoichiometry is built around on law of conservation of mass, an understanding of atomic masses. Atoms
are neither created nor destroyed during a chemical reaction.
CHEMICAL EQUATION
Chemical equations are the representation of chemical reactions.
Example: When hydrogen ( H 2 ) and oxygen ( O2 ) are going through reaction, it forms water ( H 2 O ). The
chemical equation is written as:
2 H 2 + O2 → 2 H 2 O
The plus (+) is read as “reacts with” and the arrow (→) as “produces.” Reactants is the chemical formulas
to the left of the arrow represent the starting substances. Products is the
chemical formulas to the right of the arrow represent substances produced in the reaction.
Because of the law of conservation of mass, a chemical equation must have an equal number of atoms of
each element on each side of the arrow; known as making the equation balanced.
Note that the number of atoms is obtained by multiplying each subscript in a chemical formula by the
coefficient for the formula.
While making the equation balanced, For most purposes, a balanced equation should contain the smallest
possible whole-number coefficients. Also, Never change subscripts when balancing an equation.
As an illustration, let's look at the reaction as methane ( CH 4 ) is burning in air to create carbon dioxide gas (
CO2 ) and water vapor ( H 2 O ).
CH 4 + O2 → CO2 + H 2 O (unbalanced)
CH 4 + O2 → CO2 +2 H 2 O (unbalanced)
CH 4 +2 O2 → CO2 +2 H 2 O (balanced)
Physical state of each reactant and product are shown with symbols: gases (g), liquids (l), solids (s), and
aqueous solution (aq).
For example:
CH 4 (g) +2 O2 (g) → CO2 (g) +2 H 2 O (g)
Sometimes symbols that represent the conditions under which the reaction proceeds appear above or below
the reaction arrow; like the symbol Δ (Greek uppercase delta)to indicate the reaction arrow indicates the
addition of heat.
SIMPLE PATTERNS OF CHEMICAL REACTIVITY
The combination reactions are when two or more substances react to form one product.
For example, magnesium with air to produce magnesium oxide:
2 M g (s) + O2 (g) → 2 M gO2 (s)
The decomposition reaction one substance undergoes a reaction to produce two or more other
substances.
Combustion reactions are rapid reactions that produce a flame. Most combustion reactions we observe
involve O2 from air as a reactant.
C 3 H 8 (g) +5 O2 (g) → 3 CO2 (g) + 4 H 2 O (g)
Propane burning in air
FORMULA WEIGHTS
Chemical formulas and chemical equations both have a quantitative significance in that the subscripts in
formulas and the coefficients in equations represent precise quantities.
The formula weight (FW) of a substance is the sum of the atomic weights (AW) of the atoms in the
chemical formula of the substance.
FW of H 2 SO4 = 2(AW of H) + (AW of S) + 4(AW of O)
= 98.1 amu
Molecular weight (MW) is chemical formula is that of a molecule.
MW of C 6 H 12 O6 = 6112.0 amu2 + 1211.0 amu2 + 6116.0 amu2 = 180.0 amu
Because ionic substances exist as three-dimensional arrays of ions, it is inappropriate to speak of molecules
of these substances. Instead, use the empirical formula as the formula unit, and the formula weight of an
ionic substance is determined by summing the atomic weights of the atoms in the empirical formula.
Example:
FW of CaCl2 = 40.1 amu + 2(35.5 amu)
= 111.1 amu
The elemental composition of a substance is used for calculating the percentage composition of any
element in a substance.
SECTION 4: AVOGADRO'S NUMBER AND THE MOLE
Problem Solving
1. Analyze the problem. Read the problem carefully. What does it say? Draw a picture or diagram
that will help you to visualize the problem. Write down both the data you are given and the quantity
you need to obtain (the unknown).
2. Develop a plan for solving the problem. Consider a possible path between the given information
and the unknown. What principles or equations relate the known data to the unknown? Recognize
that some data may not be given explicitly in the problem; you may be expected to know certain
quantities (such as Avogadro’s number) or look them up in tables (such as atomic weights).
Recognize also that your plan may involve either a single step or a series of steps with intermediate
answers.
3. Solve the problem. Use the known information and suitable equations or relationships to solve for
the unknown. Dimensional analysis is a useful tool for solving a great number of problems. Be
careful with significant figures, signs, and units.
4. Check the solution. Read the problem again to make sure you have found all the solutions asked
for in the problem. Does your answer make sense? That is, is the answer outrageously large or small
or is it in the ballpark? Finally, are the units and significant figures correct?
One mole is the amount of matter that contains as many objects as the number of atoms in exactly 12g of
isotopically pure 12 C .
Avogadro’s number, N A , named after Italian scientist Amedeo Avogadro (1776–1856), it is often cited with
units of reciprocal moles, 6.02 x 1023 mol−1 .
A mole is always the same number (6.02 x 10 ), but 1-mol samples of different substances have different
23
masses.
The mass of an atom to the mass of Avogadro’s number (1 mol) of these atoms: The atomic weight of an element
in atomic mass units is numerically equal to the mass in grams of 1 mol of that element.
Molar mass is the mass in grams of one mole, often abbreviated as 1 mol, of a substance (that is, the mass
in grams per mole).
The molar mass in grams per mole of any substance is numerically equal to its formula weight in atomic mass units.
Mole Relationships
EMPIRICAL FORMULAS FROM ANALYSES
The ratio of the numbers of moles of all elements in a compound gives the subscripts in the compound’s empirical formula.
The empirical formula is correct because its subscripts are the smallest integers that express the ratio of
atoms present in the compound.
The subscripts in the molecular formula of a substance are always whole-number multiples of the subscripts
in its empirical formula.
M olecular weight
W hole − number multiple = Empirical F ormula W eight
One technique for determining empirical formulas in the laboratory is combustion analysis, commonly used for
compounds containing principally carbon and hydrogen.
The use of balancing about
The coefficients in a chemical equation represent the relative numbers of molecules in a reaction. The mole
concept allows us to convert this information to the masses of the substances in the reaction.
2 H 2 (g) + O2 (g) → 2 H 2 O (l)
We can generalize this observation to all balanced chemical equations: The coefficients in a balanced chemical
equation indicate both the relative numbers of molecules (or formula units) in the reaction and the relative numbers of moles.
Stoichiometrically equivalent quantities:
LIMITING REACTANTS
Limiting reactant is the reactant that is completely consumed in a reaction because it determines, or limits,
the amount of product formed.
Theoretical yield is the quantity of product calculated to form when all of a limiting reactant is consumed.
The percent yield of a reaction relates actual and theoretical yields:
Sample Questions:
1. Interpreting and Balancing Chemical Equations: The following diagram represents a chemical
reaction in which the red spheres are oxygen atoms and the blue spheres are nitrogen atoms. (a) Write the
chemical formulas for the reactants and products. (b) Write a balanced equation for the reaction. (c) Is the
diagram consistent with the law of conservation of mass?
2. Writing Balanced Equations for Combination and Decomposition Reactions: Write a balanced
equation for (a) the combination reaction between lithium metal and fluorine gas and (b) the decomposition
reaction that occurs when solid barium carbonate is heated (two products form, a solid and a gas).
3. Calculating Formula Weights: Calculate the formula weight of (a) sucrose, C 12 H 22 O11 (table sugar);
and (b) calcium nitrate, Ca(N O3 )2 .
4. Calculating Percentage Composition: Calculate the percentage of carbon, hydrogen, and oxygen (by
mass) in C 12 H 22 O11 .
5. Estimating Numbers of Atoms: Without using a calculator, arrange these samples in order of
increasing numbers of carbon atoms: 12g 12 C , 1 mol C 2 H 2 , 9* 1023 molecules of CO2 .
6, Converting Moles to Number of Atoms: Calculate the number of H atoms in 0.350 mol of C 6 H 12 O6 .
7. Calculating Molar Mass: What is the molar mass of glucose, C 6 H 12 O6 ?
8. Calculating an Empirical Formula: Ascorbic acid (vitamin C) contains 40.92% C, 4.58% H, and
54.50% O by mass. What is the empirical formula of ascorbic acid?
9. Determining a Molecular Formula: Mesitylene, a hydrocarbon found in crude oil, has an empirical
formula of C3H4 and an experimentally determined molecular weight of 121 amu. What is its molecular
formula?
10. Calculating Amounts of Reactants and Products: Determine how many grams of water are produced
in the oxidation of 1.00 g of glucose, C 6 H 12 O6 :
Chapter 7 : Gases
The ideal gas law defines the relationship among the volume, pressure, temperature, and moles of gas. Also
the kinetic molecular theory is used to describe the behavior of the gases. Pressure is the amount of force
applied to an area:
P = F/A
*Atmospheric pressure is the weight of air per unit of area.
Units of Pressure
The lists below are the units that expresses pressure :
Pascals: 1 Pa = 1 N/m2 (SI unit of pressure)
Bar: 1 bar = 105 Pa = 100 kPa
mm Hg or torr: The difference in the heights measured in mm of two connected columns of mercury
Atmosphere: 1.00 atm = 760 torr = 760 mm Hg = 101.325 kPa
Boyle’s Law
Boyle’s Law describes the inverse pressure-Volume relationship. The volume of a fixed quantity of gas at
constant temperature is inversely proportional to the pressure.
Also PV is a constant so if we compare two conditions, it should be:
P1V1 = P2V2
Charles’s Law
Charles’s law describes the temperature-volume relationship. The volume of a fixed amount of gas at
constant pressure is directly proportional to its absolute temperature. And the equation will be :
V = constant * T
Avogadro’s Law
By the Avogadro’s law, the volume of a gas at constant temperature and pressure is directly proportional to
the number of moles of the gas.Also, at STP, one mole of gas occupies 22.4 L. The equation will be
V = constant * n
Ideal-Gas Equation
Combining Boyle’s law, Charles’s law and Avogadro’s law we get V ∝ (nT)/P , and if we use a constant of
proportionality (R) and reorganize; this gives the Ideal-Gas Equation:
PV = nRT.
Density & Molar Mass of a Gas
One needs to know only the molecular mass, the pressure, and the temperature to calculate the density of a
gas(d = MP/RT). Also, if we know the mass, volume, and temperature of a gas, we can find its molar mass
(M = mRT/PV).
Volume and Chemical Reactions
The balanced equation tells us relative amounts of moles in a reaction, whether the compared materials are
products or reactants (PV = nRT)
Dalton’s Law of Partial Pressures
Dalton’s new law of partial Pressures states that two gases that don’t react are combined in a container, they
act as if they are alone in the container. The total pressure of a mixture of gases equals the sum of the
pressures that each would exert if it were present alone. So the equation will be :
Ptotal = p1 + p2 + p3 + …
Mole Fraction
The ratio of moles of a substance to total moles is called the mole fraction, X :
X = (Moles of compound 1)/ Total metals
Kinetic molecular theory
The kinetic molecular theory describes gases at the level of individual particles. This is stated as :
1. Gases consist of molecules or atoms in continuous random motion.
2. Collisions between these molecules and/or atoms in a gas are elastic
3. The volume occupied by the atoms and/or molecules in a gas is negligibly small.
4. The attractive or repulsive forces between the atoms and/or molecules in a gas are negligible.
5. The average kinetic energy of a molecule or atom in a gas is directly proportional to the Kelvin
temperature of the gas.
This also explains Graham’s law of effusion.
Sample Questions
1. Considering Boyle's la if the pressure is reduced, a gas will increase in
A) volume
B) temperature
C) average kinetic energy
D) effusion rate
2. If methane, CH4, rather than ethane, CHaCH, is the gas used under comparable conditions, there will be
an increase in
A) volume and average kinetic energy
B) temperature
C) average kinetic energy and pressure
D) effusion rate
3. The kinetic molecular theory postulates a direct relationship between
A) increased volume and increased average kinetic energy
B) increased temperature and increased average kinetic energy
C) increased average kinetic energy and increased pressure
D) increased effusion rate and increased pressure
4. Which of the following pairs are inversely proportional to each other, assuming all other conditions are
kept constant?
A) Volume, pressure
B) Temperature, average kinetic energy
C) Average kinetic energy, pressure
D) Effusion rate, temperature
5. A gas will behave more like an ideal gas if we have an and an
A) increased volume, increased temperature
B) increased temperature, increased average kinetic energy
C) increased average kinetic energy, increased pressure
D) increased effusion rate, increased pressure
6. what volume will 2.50 mol of N2 occupy at 45 "Cand 1.50 atm of pressure? (
A) 43.5 L
B) 6.08 L
C) 0.0233 L
D) 56.00 L
7. How many moles of helium are needed to fill a balloon that has a volume of 6.45 Land a pressure of 800
mm Hg at a room temperature of 24 "O? Assume ideal gas behavior. (
A) 0288
B) 214
C) 0.278
D) 2.65 x 103
8. What will the total pressure be in a2.50-L flask at 25 oc fit contains oo16 mol of co2 and 0.035 mol of
CH4?
A) 31.4 mm Hg
B) 380 mm Hg
C) 0.041 mm Hg
D) 935 mm Hg
9. In which of the following is it impossible to predict whether the pressure of a gas will increase, decrease,
or stay the same?
A) A gas sample is heated.
B) A gas sample is heated, and the volume is increased.
C) A gas sample is cooled, and some gas is withdrawn.
D) Additional gas is added to a sample of gas.
14. The kinetic molecular theory predicts that at a given temperature
A) all gas molecules have the same kinetic energy
B) all gas molecules have the same average velocity
C) only real gas molecules collide with each other
D) on the average, heavier molecules move more slowly
Answers and Explanations
1. (A) Boyle's law says that P x v constant. Therefore as the pressure decreases the volume must increase.
2. (D) The effusion rate will increase if the molecular mass is decreased, as it does going from ethane to
methane.
3. (B) The relationship between temperature and average kinetic energy is a fundamental principle.
4. (A) volume and pressure change in opposite directions because they are inversely proportional. All other
pairs are directly proportional to each other.
5. (A) The more volume per molecule keeps them widely separated, therefore reducing interactions.
Increased velocity due to an increased temperature also reduces attractions between gas molecules.
6. (A) This problem gives all of the information needed to solve the ideal gas law equation, PV nRT, for
volume:
V=(nRT)/P = 43.5L
All of the values given in the problem are used directly in this equation except that the temperature of 45’C
must be converted to 318 K The other choices represent incorrect combinations of the given data.
7. (c) This is a calculation using the ideal gas law equation : n =(PV)/(RT)
0.275mol
8. (B) This is solved by using the ideal gas laws. PV = nRT
0.343atm and using dalton’s law of partial pressure
Total pressure = 0.157 + 0.343 = 0.500 atm
9. (B) Heating a gas increases the pressure, while increasing the volume decreases the pressure. From the
information given, it is impossible to tell whether the temperature increase will and cause an increase in
pressure or whether the volume increase dominate will dominate and cause an overall pressure decrease. All
of the other options will definitely cause either an increase or a decrease in pressure of the gas.
10. (D) On the average, heavier molecules move more slowly
Chapter 8: Liquids and Solids
SECTION 1: A MOLECULAR COMPARISON OF GASES, LIQUIDS, AND SOLIDS
Intermolecular forces refer to the forces between molecules. These forces determine the physical
characteristics of different substances (gases, liquids, and solids).
In this chapter we will have a close look at liquids. Liquids and solids have stronger intermolecular force
than that of gases. They are condensed phases-they are denser and harder to compress than gases because
there is not much free space between particles.
Gas ● Kinetic energies > Energies of attraction
● Flows freely to fill its container and assumes the volume and shape
of it
● Compressible
● Rapid diffusion
In the image above, the phase changes with red arrows are endothermic (energy is added to substance) and
the phase changes with blue arrows are exothermic (energy is released).
Critical temperature is the highest temperature which a liquid can exist, and the critical pressure is the
pressure required to retain the liquid phase at this critical temperature. The greater the intermolecular forces,
the higher the critical temperature.
Superficial fluid refers to a state which the liquid and gas are indistinguishable. When the temperature is
above the critical temperature and the pressure is above the critical pressure, a superficial fluid is formed.
Like gases, a substance flows to fill its container but the molecules are still close to each other like liquids.
SECTION 5: VAPOR PRESSURE
Vapor pressure refers to a pressure exerted by vapor when a substance is evaporating.
When a substance is in simultaneous, opposing processes (such as evaporation and liquefaction), the
condition is called dynamic equilibrium. The vapor pressure of the liquid and the gas are the same when
the substance is in dynamic equilibrium,.
Liquids with high vapor pressure are easier to evaporate and are called volatile.
Normal boiling point refers to the boiling point of a liquid at 1 atm (760 torr). The higher the pressure,
the lower the boiling point.
PHASE DIAGRAMS
the phase diagram above, the blue curve is the vapor-pressure curve, which shows the dynamic
equilibrium of liquid and gas phases. Point C is a critical point of a substance. The point is at the critical
temperature and critical pressure of the substance. At the area beyond point C, the substance becomes a
supercritical fluid.
The red curve is the sublimation curve of a substance. The point on this curve represents the dynamic
equilibrium of solid and gas phases.
The green curve is the melting curve of a substance. Like the normal boiling point, the melting point at 1
atm is called the normal melting point.
At triple point, all three phases are in dynamic equilibrium. Any point that is not on any of those curves
means that a substance is in only one phase.
SOLIDS
The solid on the right is obsidian, one of the amorphous solids. Amorphous solids have irregular patterns
on their surface and are considered noncrystalline.
The solid on the left is halite, one of the crystalline solids. Crystalline solids have flat surfaces with a
repeating pattern (such as cube). The repeating unit is called a unit cell. There must be no gap between the
unit cells (in other words, the lattices must be “tiled”).
Metallic solids are composed of metal atoms. They are cold when touched, but they have high thermal
conductivity and high electrical conductivity. Also, most of them are malleable and ductile (can be drawn
into wires). In general, thermal conductivity and electrical conductivity for metals are positively correlated.
The bond between these atoms is called metallic bonding. Because of strong dispersion forces, the metallic
bonding is also strong. The valence electrons of these atoms are delocalized, meaning that the electrons are
freely spread within the entire solid.
Alloy is a substance with characteristics of a metal but containing more than one element. There are two
types of alloys: substitutional alloys and interstitial alloys. Elements in substitutional alloys have similar
atomic radii and characteristics. Interstitial alloys, in general, are composed of one nonmetal element and
one metal element, forming covalent bonds.
Ionic solids are made by the ionic bonds between cations and anions. According to Coulomb’s law,
q₁q₂/r, the strength of the attraction is directly proportional to the charges of the ions and inversely
proportional to the distance between the ions. Unlike metallic solids, ionic solids are brittle.
Molecular solids are composed of nonmetal elements. The atoms are held together by covalent bonds and
intermolecular forces. In general, molecular solids are softer and have lower melting points.
In covalent-network solids, atoms are bound to each other covalently. A diamond and a graphite are
examples of covalent-network solids.
Sample questions
1. List the following intermolecular forces from the weakest to the strongest: dipole-dipole, dispersion, and
hydrogen bonds.
2. Which of the following have the highest melting points?
a) Metals
b) Salts
c) Molecular solids
d) Alkanes
3. Which of the following compound will not form hydrogen bonds?
a) CH₂F₂
b) CH₃OH
c) H₂NCH₂CH₂CH₃
d) HOCH₂CH₂OH
4. Which of the following statements is not consistent with the crystal properties of the substance?
a) SiC is used to grind metal parts to shape.
b) Tungsten is drawn into thin wires.
c) Aluminum is used to cut glass.
d) Graphite is used to lubricate locks.
5. What causes C30H6 2 to be a nonpolar compound that is a solid at room temperature?
a) Ionic bonds
b) Dipole-dipole forces
c) Dispersion forces
d) The fact that C30H6 2 is a heavy molecule
6. When the following compounds are kept at the same temperature, the compound expected to evaporate
most quickly is
a) C8H1 8
b) C8H1 7OH
c) C8H1 7NH2
d) C8H1 4
7. Which of the following is expected to have the lowest vapor pressure?
a) C6H1 3OH
b) C8H1 7OH
c) C3H7 OC3H7
d) C6H1 2
8.A liquid substance that exhibits low intermolecular forces is expected to have
a) low viscosity, low boiling point ,and low heat of vaporization
b) high viscosity, low boiling point ,and low heat of vaporization
c) low viscosity, high boiling point ,and low heat of vaporization
d) low viscosity, low boiling point ,and high heat of vaporization
9. Calculate the enthalpy change upon converting 1.00 mol of ice at -25℃ to steam at 125℃ under a
constant pressure of 1 atm. The specific heats of ice, liquid water, and steam are 2.03, 4.18, and 1.84J/g-K.
For water, ∆Hfus = 6.01kJ/mol and ∆Hvap = 40.67kJ/mol for water.
In the heating curve on the left, the temperature is constant
for the section BC (melting or fusion) and DE
(vaporization), where the phase changes are occuring.
The increased freedom of motion of the particles within the
substance is the heat of fusion or enthalpy of fusion,
written as ∆Hfus. ∆Hfus of an ice is 6.01kJ/mol. ∆Hvap,
also known as either the heat of vaporization or the
enthalpy of vaporization, is 40.7kJ/mol for water. The heat
of sublimation, or ∆Hsub is 47kJ/mol for water.
10.
Use the phase diagram of methane to answer the following questions.
a) What is the normal boiling point of methane?
b) Over what pressure range does solid methane sublime?
c) Above what temperature does liquid methane not exist?
ANSWERS.
1. dispersion forces, dipole-dipole forces, and hydrogen bonds
2. (b). Ionic bonds are the strongest among the intramolecular forces.
3. (a). If we look at the structure of CH₂F₂, the hydrogen atoms are attached to the carbon atom. In order
to form hydrogen bonds, hydrogen atoms must be bound to strongly electronegative atoms, such as
nitrogen, oxygen, and fluorine.
4. (c). In general, molecular solids are softer than other solids.
5. (c). There are no ionic bonds in C30H6 2. Since C30H6 2 is nonpolar, dipole-dipole forces cannot exist.
6. (d). C8H1 4 is the lightest.
7. (a). Because hydrogen atoms in C6H1 3OH are bonded to the oxygen atom, C6H1 3OH forms hydrogen
bondings, which is the strongest intermolecular force
.
8. (a). Viscosity refers to the resistance to flow. The weaker the intermolecular forces, the lower the heat of
vaporization and boiling point.;
18.0g
9. AB : 1.00mol · mol · 2.03J g−K · 25K = 914J = 0.91kJ
B C : 1.00mol · 6.01kJ
mol = 6.01kJ
18.0g 4.18J
C D : 1.00mol · mol · g−K · 25K = 7520J = 7.52kJ
DE : 1.00mol · 40.67kJ
mol = 40.7kJ
18.0g 1.84J
E F : 1.00mol · mol · g−K · 25K = 830J = 0.86kJ
∆H = 0.91kJ + 6.01kJ + 7.52kJ + 40.7kJ + 0.83kJ = 56.0kJ
10. (a) Approximately -160℃
(b) It sublimes when the pressure is below 10-1 atm.
(c) The vapor-pressure curve ends at the temperature -80℃. Therefore, we can say that liquid methane
cannot be found when the temperature is above 80℃.
Chapter 9: Properties of Solutions
THE SOLUTION PROCESS
Homogeneous mixtures, substances that are mixed evenly in a solvent, are called solutions. When there are
strong intermolecular forces between the solvent and the solute, it is likely that the solute will dissolve.
There are three kinds of intermolecular interactions that affect a solution process:
● Solute-solute interaction: attraction between solute particles. It must break so the solute particles
can disperse.
● Solvent-solvent interaction: attraction between solvent particles. There must be space between
solvent particles so the solute particles can dissolve.
● Solvent-solute interaction: attraction between solvent particles and solute particles. It must exist in
order to form a solution.
The process of making a solution is solvation. When the solvent is water, the process is called hydration.
According to Hess’s law, ∆Hsoln = ∆Hsolute+ ∆Hsolvent + ∆Hmix.
For exothermic solution processes, ∆Hsoln is negative, and for endothermic solution processes, ∆Hsoln is
positive. ∆Hsoln is the change in enthalpy of a solution (measured in kJ/mol), ∆Hsolute is the change in
enthalpy of a solute (solute particles are separated), ∆Hsolvent is the change in enthalpy of a solvent (solvent
particles are separated as well), and ∆Hmix is the change in enthalpy of mixture of a solute and a solvent.
A polar substance (such as water) and a nonpolar substance (such as octane) cannot be mixed. Also, an ionic
solute (such as salt) and a nonpolar solvent cannot be mixed because of the large disparity between the
solute-solute interaction and solvent-solvent interaction.
SOLUBILITY
Solubility can be increased if the pressure and/or temperature increases. However, the solubility of gases in
water decreases if the temperature increases.
A solution is saturated when the solute is not completely dissolved. If a solute is completely dissolved, the
solution is unsaturated. Solubility refers to the amount of solute required to form a saturated solution of a
given amount of solvent. When a solution dissolves solute more than the amount it can dissolve, the
solution is supersaturated. A solution can be supersaturated under a high temperature or pressure.
Liquids that can be mixed in all proportions, such as acetone and water, are miscible.
Alcohol with the polar OH groups is soluble in water because it is able to form hydrogen bonds with water
molecules. However, the presence of the OH groups does not guarantee that the solute will dissolve in
water. For instance, vitamin A has one OH group, but it is fat-soluble because most of its molecules are
non-polar. By contrast, vitamin C is water-soluble because it has more OH groups than vitamin A.
By contrast, liquids that cannot be mixed, such as nonpolar liquids in polar liquids, are immiscible.
Solubilities of Some Alcohols in Water and Hexane
C H 3 OH (methanol) ∞ 0.12
C H 3 CH 2 OH (ethanol) ∞ ∞
C H 3 CH 2 CH 2 OH (propanol) ∞ ∞
C H 3 CH 2 CH 2 CH 2 OH (butanol) 0.11 ∞
C H 3 CH 2 CH 2 CH 2 CH 2 OH (pentanol) 0.030 ∞
C H 3 CH 2 CH 2 CH 2 CH 2 CH 2 OH (hexanol) 0.0058 ∞
Henry’s law represents the relationship between pressure and solubility (gas).
Sg = kPg
Sg is the solubility of the gas in the solvent (expressed as molarity), Pg is partial pressure, and k is a constant.
Raoult’s law, visualized
Vapor pressure is exerted when a liquid and a gas are in dynamic equilibrium. However, a nonvolatile
substance exerts no vapor pressure. A volatile substance exerts vapor pressure. Raoult’s law shows the
direct relationship between the vapor pressure of a volatile solvent above a solution containing a nonvolatile
solute.
Psolution = Xsolvent × P°solvent
Psolution is the partial pressure exerted by evaporated solvent above the solution. Xsolvent is the mole
fraction of the solvent. P°solvent is the vapor pressure of the pure solvent.
SOLUTION CONCENTRATION
Mass percentage represents how much solute is present for each 100g of solution. For example, 80% HCl
contains 80 g of HCl of each 100 g of solution.
Parts per million (ppm) represents how much solute, in grams, is present for each million grams of
solution, or how much solute, in milligrams, is present for each kilogram of solution.
Mole fraction of component shows the proportion of moles of solute in its solution and has no units. For
always, sum of the mole fractions of all components is 1.
Molarity (M) shows how many moles of solute are present for each liter of solution.
Molality (m) shows how many moles of solute are present for each kilogram of solvent.
mass of component in solution
Mass percentage = total mass of solution · 100%
mass of component in solution
ppm (parts per million) of component = total mass of solution · 10 6
moles of component
Mole fraction of component = total moles of all components
moles of solute
Molarity (M) = liters of solution
moles of solute
Molality (m) = kilograms of solvent
(Tip: remember the common consonants. Molarity, Liters)
OSMOSIS
Osmosis refers to the process by which water moves according to the concentration gradient.
n
Π = i( V )RT = iMRT
Π is the osmotic pressure, the pressure that stops osmosis. i is the van’t Hoff factor (it is 1 if the substance
is a nonelectrolyte), V is the volume of the solution, n is the number of moles of solute, R is the ideal-gas
constant (0.0821L-atm/mol-K), T is the absolute temperature, and M is the molarity of the solution.
Two solutions are isotonic if they have the same osmotic pressure. If one has a lower osmotic pressure, it is
hypotonic. The one with a higher osmotic pressure, or concentration, is hypertonic.
Sample question
1. Arrange the following substances in order of increasing solubility in water.
2. Calculate the concentration CO2 of in a soft drink that is bottled with a partial pressure of CO2 of 4.0
atm over the liquid at 25℃. The Henry’s law constant for CO2 in water at this temperature is 3.4 · 10−2
mol/L-atm.
3. Glycerin (C₃H₃O₃) is a nonvolatile nonelectrolyte with a density of 1.26g/mL at 25℃. Calculate the
vapor pressure at 25℃ of a solution made by adding 50.0 mL of glycerin to 500.0 mL of water. The vapor
pressure of pure water at 25℃ is 23.8 torr, and its density is 1.00g/mL.
1.26g
50.0ml · 1mL · 192.1g
mol
= 0.684mol C₃H₃O₃
1.00g 1 mol
500.0mL · 1mL · 18.0g = 27.8 mol H₂O
4. A solution with a density of 0.876g/mL contains 5.0g of toluene (C7H8) and 225g of benzene. Calculate
the molarity of the solution.
5.0 g · 192g
mol
= 0.054 mol toluene
1mL
230g · 0.876g = 263 mL solution
5. A solution is made by dissolving 13.5 g of glucose (C6H12O6) in 0.100 kg of water. What is the mass
percentage of solute in this solution?
6. A 2.5g sample of groundwater was found to contain 5.4 μg of Zn2+. What is the concentration of Zn2+
in parts per million?
7. An aqueous solution of hydrochloric acid contains 36% HCl by mass. Calculate the mole fraction of HCl
in the solution.
36g · 136.5g
mol
= 0.99 mol HCl
1 mol
64g · = 3.6 mol H₂O
18g
. An aqueous solution of hydrochloric acid contains 44% HCl by mass. Calculate the molality of HCl in the
solution.
1 mol
44g · 36.5g= 1.20 mol HCl
Water is 56g = 0.056kg.
9. Is the osmotic pressure of a 0.10 M solution of a NaCl greater than, less than, or equal to that of a 0.10 M
solution of KBr?
10. The average osmotic pressure of blood is 7.7 atm at 25℃. What molarity of glucose (C6H12O6) will be
isotonic with blood?
Answers
1. a, d, b, c
(a) is nonpolar. The OH groups in (b) and (c) are more polar than the Cl atom in (d). (c) has more OH
groups than (b).
2. SCO2 = kPCO2 = (3.4*10^-2 mol/L-atm) (4.0 atm) = 0.14 mol/L = 0.14 M
3. Using the formula Psolution = Xsolvent · P°solvent,
27.8
XC₃H₃O₃ = 27.8+0.684 = 0.976
PH₂O = Xsolvent · P°solvent = 0.976 · 23.8 torr = 23.2 torr
4. 0.054mol
263mL ·
1000mL
L = 0.21 M
13.5g
5. 13.5g+100g · 100% = 11.9%
−6
6. 10 6 · 5.4·10
2.5g = 2.2 ppm
0.99
7. Mole fraction of HCl = 3.6+0.99 = 0.22
1.2 mol HCl
8. 0.056kg H2O = 21 m
9.Both the NaCl solution and the KBr solution have the same osmotic pressure. Because they have the same
concentration (M), they are osmotic.
n
10. Π = i( V )RT = iMRT
Π 7.7atm
M = iRT = (1·0.0821L−atm/mol−K)·298K =0.31 M
Cl2
The exponent for CO will be calculate using the same method but with values from experiments 2 and 3.
Rate2
E xponent of CO = Rate
CO1
1
CO2
THE ORDER OF A REACTION
Until now, the variables X and Y were described as “exponents”. However, in chemistry, the addition of
those two variables are described as the order of the reaction.
There are 3 distinct orders that is needed for the AP exam: Zero Order, First Order, Second Order.
Zero Order Reaction
In a zero order reaction, the addition of the two variables will equate zero so,
Rate = K
For zero order reactions, the graph of time to concentration of a particular reactant will be linear,
First Order Reaction
In a first order reaction, the addition of the two variable will equate to 1 so,
Rate = K[A]
For a first order reaction, the graph of time to the natural log of the concentration of the reactant will be
linear,
Second Order reaction
In a second order reaction, the addition of the two variables will equate to 2 so,
Rate = K[A][B]
For a second order reaction, the graph of time to the inverse of the natural log of the concentration of the
reactant will be linear,
*It is important to memorize the shape of the graphs for each order of reaction. The AP exam often asks
question where you need to determine the order of the reaction only by looking at 3 graphs of concentration
to time graphs
EASIER WAY
While getting the order and determining the rate law through experiments can prove to be useful in
understanding the concepts for this chapter, there is a much easier way to calculate the concentration of the
reactant any time after the reaction started.
A
ln( A0 ) = K t
t
ln(A0 ) − ln(At ) = Kt
A0 represent
the initial concentration of [A]. At represents the concentration of [A] at time = t
*Don’t worry if it is difficult to memorize the equation, the ap test provides a formula sheet, and this
equation is included in that.
Rate Laws
The AP test often gives questions on determining the correct rate law. The important aspect to remember is
that the slow reaction is the determining rate law of the overall reaction. This is because, the faster reaction
will always be dependant on the completion of the slower reaction to complete the overall reaction.
A + B → C (slow)
2A + B → C (f ast)
Rate Law: Rate = k[A][B]
Half Life
When studying reaction rate, an important part that must be learnt for the AP exam is the concept of
radioactivity. But because the exam does not go into depth of the topic, you should know radioactivity as
the tendency for an atom to emit subatomic particles and decrease in mass
The time that it takes for a atom to lose exactly half of its mass is the Half Life of a reaction. The Half life
of a reaction is given by the equation,
t1/2 = ln(2)
k
= 0.693
k
*k is the rate constant of a reaction
Theory of Reaction Rates
When studying reaction rates, there are two distinct theorie that you must know the concept of for the AP
exam
● The Collision Theory
● Transition-State Theory
The Collision Theory states the rate of the reaction depends on the actual collision between two particles.
In that, a reaction occurs as a result of the collision of two particles. Usually this is depicted by the collision
of two large balls.
The Transition-State Theory states that, in the case of a reaction, the geometric orientation of a
“intermediate” is what determines the rate of the reaction. In that, if the orientation allows for an effective
transfer of energy, which results in a higher reaction rate.
Reaction Profile
In the AP exam it is also vital for you to know and interpret the reaction profile of specific reactions. And to
recognize if the reaction is exothermic, or endothermic, and what the activation energy of the reaction is.
Identifying Exothermic and Endothermic reactions
The two graphs above show the exothermic and endothermic reaction profiles. When attempting to identify which is
which, it is vital to understand and use the following equation
ΔH = H f − H i
This equation will be discussed later, for now, ΔH is the net change in heat, Hf is the final amount of heat, Hi is
the
initial amount of heat. When ΔH is positive, we say the reaction is endothermic, when ΔH is negative we say the
reaction is exothermic.
When presented with the above graphs, the easy way to see if one is exothermic or endothermic would be to see if the
final horizontal line is above or lower than the initial line. If the line is below the initial line, the reaction is
exothermic. If the line is above initial line, the reaction is endothermic. But how do these reactions actual start in the
first place?
Identifying the activation energy of the reaction
Activation energy is, the minimum energy requirement for a reaction to actually fire. The AP exam requires test takers
to recognize the activation energy by looking at the reaction profiles. By using the previous graphs,
To recognize the activation energy of the following reaction, draw a vertical line from the initial horizontal line to the
highest point. The length of that line represents the activation energy. And as already mentioned, a catalyst will be able
to reduce this activation energy
SAMPLE QUESTIONS
1. A certain reactions rate to concentration graph is represented below. Based on the following graphs, what
order reaction is it?
a) Zero Order reaction
b) First Order reaction
c) Second Order reaction
d) Third Order reaction
2. The Initial and final concentration of Na at T=0 and T= 30 is 40M, 30M respectively. What is the
reaction rate of the following reaction?
a) 34M/s
b) 24M/s
c) -0.6M/s
d) -0.3M/s
3. It was determined that the chemical reaction A+B → C is a first order with respect to A and first order
with respect to b
Assuming the reaction to be an elementary process, which of the following statements is TRUE concerning
this reaction?
a) The molecularity and overall order are both 1
b) The molecularity is 1, while the overall order is 2
c) The molecularity is 2, while the overall order is 1
d) The molecularity and overall order are both 2
4. For the following mechanisms, which of the following is the correct Rate Law?
N O + N O → N 2 O2 (slow)
N 2 O2 + O2 → 2N O2 (f ast)
a) Rate = k[NO]2[O2]
b) Rate = k[N2O2][O2]
c) Rate = k[N2O2]
d) Rate = k[NO]2
5. The rate law of a chemical reaction was determined to be Rate = k[A]2[B]
What is the overall order of the reaction?
a) 1
b) 2
c) 3
d) 4
6. The rate law of some reaction is rate= k[A]2[B]3
Which of the following is the overall order for the reaction?
a) Second order
b) Third order
c) Fifth order
d) Sixth order
7. Which of the following can be used to measure the decrease in concentration of aqueous reactant over
time?
a) Paper chromatography
b) Spectroscopy
c) Pressure differences
d) Reduced turbidity
8. In a reaction, when A and B are both doubled, the rate goes up by a multiplication of eight. The rate law
is:
Rate = k[A]m[B]2
What is the rate order with respect to [A]?
a) First order
b) Second order
c) Third order
d) Fourth order
9. If the temperature of an exothermic reaction is increased, what happens to the reaction rate?
a) It increases
b) It decreases
c) It stays the same
d) It stops
10. For the reaction shown, which of the following Best describes the elementary reaction?
2N 2 O5 ↔ 4N O2 + O2
a) First order unimolecular
b) Second order unimolecular
c) Second order bimolecular
d) First order bimolecular
ANSWERS
1. (B) as the graph of ln[A] is linear, this gives evidence that the reaction is a first order reaction
2. (D) 30-60/30-0 gives the answers of -0.3, we do this as the change or concentration over change in time
gives the reaction rate
3. (D) molecularity is basically the number of reactants, as there are two, molecularity is two. As the
coefficients are each 1, the order is 2
4. (D) as the above reaction is the slower one and as such, the rate determining reaction
5. (C) add 1 and 2 and we get 3, resulting in a third order reaction. The values 1 and 2 come from the
individual exponents from each species
6. (C) add 2 and 3 and we get 5, showing a fifth order reaction
7. (B) spectroscopy will show us the change in the concentration over a time frame. The other methods
gives us nothing about the change in concentration, and as such, nothing about the reaction rate
8. (A) if we first multiply A and B by 2, we can then multiply one by 2 which gives us 4. And as such, fi we
keep M and 1, we result with a coefficient of 8
9. (B) As the reaction is exothermic, an addition of heat will make it difficult for the reaction to transfer heat
to the surrounding, and as such, reduce the overall reaction rate
10. (C) the reaction is second order as if we add the coefficients, we get a two. And it is bimolecular as two
species are used in the reaction
Chapter 12: Thermodynamics
Thermodynamics refers to the study of how heat is transferred from one place to another and what form it
is transferred in.
In this portion we will mainly focus on relationships of chemical reactions involving energy changes that
involve heat also called thermochemistry
What is Energy?
Energy is the capacity to do work or transfer heat
Work is the energy used to cause an object to move against a force
Heat is the energy used to cause the temperature of an object to increase
Different Types of Energy
There are two types energy: Potential and Kinetic
Potential energy refers to the energy contained by an object because of its position.
Kinetic energy refers to the energy of motion. It could also be represented by the equation
E k = 12 mv 2
The picture on the left contains a lot of potential energy and less kinetic energy. The picture on the right
contains a lot of kinetic energy and less potential energy.
Units of Energy
Joules, or expressed in J, is the SI unit for energy. Joules can be also expressed as 1 J =
1Kg − m2 /s2
Another unit for energy are calories or written as (cal) and 1 calorie is about 4.184 J.
Analyzing Transfer of Energy
When people analyze transfer of energy, there are two components. The system and the surroundings. The
system is the part that is in study. The surroundings is everything else.
There are three types of systems: open, closed, or isolated
Open system: Where matter and energy can be exchanged freely from the surroundings
Closed system: Systems that can exchange energy but not matter with the surroundings
Isolated system: Where neither matter nor energy can’t be exchanged with the surroundings
First Law of Thermodynamics
The First Law of Thermodynamics states that energy can be neither created nor destroyed.
ΔE = q + w
q(Heat) (++)Heat is added to the system (---)Heat is released from the
system
Enthalpy(Internal Energy) (---)The system lost energy (++)The system gained energy
Work
Work is defined as the force applied to an object as it moves a certain distance. Work can be defined by the equation
Work = Force × Distance moved. Since Force can be defined by pressure on a given area the equation
could also be changed into Work = Pressure × Area × Distance moved. However when we apply work
to pressure volume work the equation changes to Work = Pressure × Volume Change
Prefixes Endo and Exo
Chemical reactions that release heat to the surroundings are called exothermic and chemical reactions that
absorb heat from the surroundings are called endothermic. If the sign on ΔH is positive, it indicates an
endothermic reaction. If the sign on ΔH is negative, it indicates an exothermic reaction.
Enthalpies of Reactions
An enthalpy of a reaction describes the heat involved in a reaction. It is represented as ΔH rxn.
To calculate enthalpy using a products and reactants, you can basically subtract the enthalpies of the
products minus the enthalpies of the reactants. ( ΔH = ΔH products - ΔH reactants ) For example looking at the
reaction 2H2 (g) + O2 (g) → 2H2O (g) ΔH rxn = -483.6 kJ
The ΔH rxn. tells us the amount of heat involved in the reaction. Since the value of ΔH is negative, you can
tell that the enthalpy of the products was less than the reactants and the overall reaction is exothermic. The
reactions equations that show the reaction and the enthalpy of the reaction are called thermochemical equations.
Hess’s Law
Hess’s Law states that if a reaction involves multiple steps, the enthalpy change for the overall reaction is the
sum of the enthalpies of the individual reactions. Some reactions like the combustion of methane have to
go through two processes instead of just one reaction.
For this reaction above, the enthalpies of the first two reactions add up to the overall reaction at the end.
Rules for Hess’s Law
1. When the coefficients of the molecules are multiplied by a certain constant, the enthalpy of the
reaction has to be also multiplied by the same constant.
2. When equations are reversed, and reactants become products visa versa, the signs of the enthalpies
also have to be reversed
3. The step reactions have to add up to the overall reaction by crossing out molecules that are on both
sides of the equation
Heat of Formation
Heat of formation( ΔH F )or enthalpy of formation is the change in enthalpy when a mole of a substance is
formed from small pure substituents at standard state. A standard state is defined as a molecule under 298
Kelvin and a pressure of 1 atm. Heat formation of any elements are zero because there is no energy
accompanied. For example, the heat of formation for O2 is zero but the heat of formation of O3 142.7
kJ/mol .
We can also apply this concept to Hess’s law. To calculate the heat formation of a whole reaction, it is heat
of formation of the products minus the heat of formation of the reactants represented by the equation: ΔH
rxn = Σ n
ΔH f(products) - Σ n ΔH f(reactants)
Lastly, if there are stoichiometric coefficients in front of the molecules you should multiply them with the
heat of formation.
The Second Law of Thermodynamics
The Second Law of Thermodynamics states that the state of entropy of the entire universe, will always
increase over time.
Entropy is defined as the number of ways in which a system can arrange the particles within the system.
For example a system that contains 7 moles of gas particles will generally have less entropy than a system
that contains 8 moles of gas because it has less possibilities to arrange itself. Solids generally have less
entropy than liquids and liquids have less entropy than gases.
Factors that increase entropy
1. Increase in the number of particles inside a system
2. Increase in volume
3. Changing states from a liquid to gas
4. Increase in temperature
Like the heat of formation, calculating change in entropy of a reaction can be expressed by the equation
ΔS ° = ΣS ° products - ΣS ° reactants
A positive sign on entropy indicates more randomness after a reaction and a negative sign on entropy
indicates more orderliness after a reaction.
Gibbs Free-Energy
The name Gibbs Free-Energy was named after the physical chemist J. Willard Gibbs. Gibbs Free-Energy
describes the energy left after a chemical reaction. We can express Gibbs Free-Energy using the two
variables we talked about: Enthalpy and Entropy.
Δ G ° = Δ H ° - T ΔS °
This equation closely tied to the second law of thermodynamics.
Spontaneous and Non-spontaneous
Spontaneous reactions are reactions that proceed with outside intervention.
Non-spontaneous reactions are reactions that proceed with outside intervention.
For example, and egg cracking could be a spontaneous reaction but putting the broken shells back together
would be non-spontaneous.
Reactions that have negative Gibbs Free - Energy are thermodynamically favorable or a spontaneous
reaction.
Reactions that have positive Gibbs Free-Energy are not thermodynamically favored or nonspontaneous
Although we can get Gibbs Free-Energy using enthalpy and entropy, we can get it using individual values
for Gibbs Free-Energy for different molecules. The equation would be:
ΔG ° = ΔG ° products - ΔG ° reactants
We could also get Gibbs-Free Energy using the equilibrium constant K.
ΔG ° = -RT lnK where R is the gas constant.
SAMPLE PROBLEMS
1. Calculate Δ G ° of a reaction with Δ H ° = -500kJ and Δ S ° = 100 J/K at 50 ° C. Which of the following
indicates if the reaction is spontaneous and its Δ G ° value?
(a) Δ G ° = -32,800kJ
The reaction is spontaneous
(b) G ° = -32,800kJ
Δ
The reaction is spontaneous
(c) Δ G ° = -532kJ
The reaction is not spontaneous
(d) Δ G ° = -532kJ
The reaction is spontaneous
2. Which of the following systems would BEST describe a spontaneous reaction?
(a) Immediate reaction between the substances to form products at a fast rate
(b) A reaction that occurs without any outside influence to form products
(c) A thermodynamically favored system with the release of free energy
(d) A high rate of collisions between reactant particles to form products
3. The temperature of a system is directly related to the kinetic energy of the system and any change in the
kinetic energy. Which of the following would BEST represent a system that has had the kinetic energy cut in
half?
(a) A system that starts at 50 ° C and changes to -112 ° C
(b) A system that starts at 50 ° C and changes to 25 ° C
(c) A system that starts at 0 ° C and changes to -100 ° C
(d) A system that starts at 100 ° C and changes to 50 ° C
4. A reaction has a Δ H = -150kJ and a Δ S = +575 J/K
Based on thermodynamic values given for the reaction above, which of the following statements provides
the BEST prediction of the rate of the reaction at 200 K?
(a) The reaction is not thermodynamically favored and therefore will not occur
(b) The reaction will occur at a very slow rate based on the thermodynamic values given
(c) The reaction will occur at a very fast rate based on the thermodynamic values given
(d) The reaction rate cannot be determined by the thermodynamic values given
5. Many reactions are exothermic and undergo an increase in entropy. These types of reactions are
considered thermodynamically favorable. Which of the following accounts for why these reactions are not
seen occurring on a day-to-day basis?
(a) While the reactions are thermodynamically favorable, they may have a very high activation energy
(b) While the reactions are thermodynamically favorable, they may have a very low activation energy
(c) While the reactions are thermodynamically favorable, they may only occur very slowly over time due
to high interactions
(d) These reactions are actually happening too quickly for us to see on a day-to-day basis
6. A reaction has the following date: Δ H = -5400kJ/mol and Δ S = 3700 J/mol-K. Based on the data,
which of the following statements best describes the above system?
(a) Since the reaction is exothermic and has a high entropy, the reaction is spontaneous and will occur
at a fast rate
(b) Despite the exothermic nature of the reaction and the increase in disorder, the reaction may not be
kinetically favorable, which may result in little or no product formed
(c) The data support both the thermodynamic and kinetic favorability of the reaction, indicating both a
spontaneous reaction and a fast rate of reaction
(d) The reaction will only be spontaneous at lower temperatures since the enthalpy is so high
7. The formation of diamonds is a spontaneous reaction that occurs slowly over time. Which of the
following would explain this spontaneous reaction?
(a) The reaction is thermodynamically favorable
(b) The reaction is thermodynamically unfavorable
(c) The reaction involves no activation energy
(d) The reaction involves a low activation energy
8. Which of the following correctly relates the equilibrium constant, K, with a positive Gibbs free energy
value?
(a) A more positive Δ G ° value results in a corresponding equilibrium constant of less than one
(b) A more positive Δ G ° value results in a corresponding equilibrium constant of greater than one
(c) A more positive Δ G ° value results in a corresponding equilibrium constant of equal to one
(d) The equilibrium constant cannot be directly related to Gibbs free energy
9. Work and heat energy are always viewed from the perspective of the system. Which of the following
BEST describes why this is done?
(a) Only the system can have work done on it since the surroundings are too large and complex
(b) Only the system can have heat transferred into or out of it since monitoring heat transfer in the
surroundings is difficult
(c) Sine work can be done on either a system or surroundings, using the system view is only possible for
a simple system
(d) Measuring heat transfer and temperature differences is more accurate due to the ease with which a
system can be controlled
10. The internal energy of a substance will show the largest increase by which of the following?
(a) Transferring energy from the surroundings to the system, while the system does work on the
surroundings
(b) Transferring heat from the system to the surroundings, while the system does work on the
surroundings
(c) Transferring energy from the surroundings to the system and doing work on the system
(d) Transferring heat from the system to the surroundings and doing work on the system
Answers:
1. d) Plug the values into this equation:
ΔG ° = ΔH ° - T ΔS ° and you will get D
2. b) A spontaneous reaction is a reaction that occurs without any outside influence
3. b), Kinetic energy is directly related to the temperature of a system. A decrease in temperature can only be
directly related to kinetic energy if the temperatures are in Kelvin. As the average kinetic energy of a system
is cut in half, the Kelvin temperature also is halved.
4. d), In this reaction, both values are both thermodynamically favorable. The release of energy and increase
in entropy would result in a - Δ G value at all temperatures; however, the reaction is still slow
5. a) While thermodynamically favorable reactions can be spontaneous, this does not describe the speed at
which that reaction can occur. Usually these reactions can be very slow due to a high activation energy
required for the reaction to proceed
6. b) The spontaneity of a reaction that a reaction occurs without outside influence. Thermodynamic data
only predicts spontaneity of a reaction, not the rate of the reaction. A spontaneous reaction is seen with a
large negative enthalpy, Δ H, and a large positive entropy, Δ S. The data shown does indicate a spontaneous
reaction.
7. b) This reaction is thermodynamically favorable since it happens with no outside force.
Chapter 13: Electrochemistry
Electrochemistry is the study of the relationship between electricity and chemical reactions.
In this chapter, oxidation and reduction will be focused. Oxidation is the loss of electrons, while reduction
in the gain of electrons Oxidation-reduction reactions are known as redox reactions.
The following is a shortcut:
LEOGER = Loss of Electrons is Oxidation; Gain of Electrons is Reduction
c
Equations that show only either the reduction or oxidation component are called half-reactions. For
instance, each reaction below is a half-reaction that is either oxidizing or reducing an element.
Oxidation : Sn2+ → S n4+ + 2e−
Reduction : 2F e3+ + 2e− → 2F e2+
There are a few steps for the balance of a redox reaction:
1. Divide the equation into oxidation half-reaction and reduction half reaction.
2. Balance them other than H and O.
3. Balance O first by adding water (H2O).
4. Balance H by adding H+.
5. Balance electrons.
Electrodes are “the two solid metals connected by the external circuit.” Anode is the electrode at which
oxidation occurs, and cathode is the electrode at which reduction occurs.
In this scenario, the electrons move from left to right, which means the electrons move from anode to
cathode.
The difference in potential energy per electrical charge is called potential difference. The unit of the
potential difference between two electrodes is volts. One volt is the potential difference required to impart
1 joule of energy to a charge of 1 coulomb 1 V = 1 J/C (One electron has a charge of 1.60 × 10−19 C.)
The energy flows from high potential energy to low potential energy. In electrode circuit, electrons flow
from anode to cathode (negative to positive).
The cell potential at standard conditions is called the standard cell potential and is written as
If you want to find Ecell, you have to subtract Ered (anode) from Ered (Cathode)
Ecell = Ered (cathode) - Ered (anode)
Practice Question:
For the Zn-Cu2+ voltaic cell, we have
Given that the standard reduction potential of Zn2+ to Zn(s) is -0.76V, calculate the Ered for the reduction
of Cu2+ to Cu:
Solution:
We have to use this formula to solve: Ecell = Ered (cathode) - Ered (anode)
Cu2+ is reduction which is cathode while Zn is oxidation which is anode
So, Ecell is equal to 1.10V and Ered (anode is -0.76V)
1.10V = X - (-0.76V)
X = 1.10V - 0.76V = 0.34V
Relative strengths of oxidizing and reducing agents:
Questions: Rank the following ions in the order of increasing strength as oxidizing agents:
Solution: < <
Ered = +0.96V < Ered = +0.80V < Ered = +1.33V
We can use this formula to find whether a given redox reaction is spontaneous:
E = Ered (reduction process) - Ered (oxidation process)
You have to subtract Ered of oxidation process from Ered of reduction process.
Questions: Determine whether the following reactions are spontaneous under standard conditions.
Solution:
(a) = (0V) - (0.34V) = -0.34V
has a negative value which tells that it’s not spontaneous.
(b) = (1.36V) - (0.54V) = +0.82V
has a negative value which tells that the reaction is spontaneous.
These kind of questions require just a simple concept of algebra.
shows the spontaneity of a process that occurs at constant temperature and pressure
, where
<Section 6>
The Nernst Equation
ΔG =
ΔG is “related to the standard free-energy change for the reaction."
Concentration cell: A cell based solely on the emg generated because of a difference in a concentration
When Copper has to migrate from anode to cathode, it has to move via electrolyte
Between anode, electrolyte, and cathode, current collectors should be there to make electrons possible to
flow.
Voltaic cells that perform this conversion using conventional fuels, which results in creating a fuel cell.
On the left (anode), hydrogen comes in and goes out and some of it move to the right (cathode). On the
right (cathode), however, oxygen comes in and when the oxygen and hydrogen meet, they turn into water
(H2O) and it goes out. This whole process causes electric power.
There are also two aspects that utilize the concept of fuel cells.
● Cathodic Protection
● Sacrificial Anode
Cathodic protection: protecting a metal from corrosion by making it the cathode in an electrochemical cell
Sacrificial anode: the metal that is oxidized while protecting the cathode is called the sacrificial anode.
In soil, where pipe is buried in, corrosion can be occured. In this case, the sacrificial metal plays a role as the
anode and the pipe or tank experiences cathodic protection.
Electrolysis: a technique that uses a direct electric current to drive an otherwise non-spontaneous chemical
reaction.
An electrolysis cell is made up of two electrodes immersed either in a molten salt or in a solution. Electrical
energy like a battery acts as an electron pump (pushing electrons into one electrode and pulling them from
the other).
Quantity of charge (coulombs) = current (amperes) x time (seconds)
> A coulomb is the quantity of charge passing a point in a circuit in 1 second when the current is 1 ampere
(A)
The Hall-Heroult process
Bronsted Lowry Definition Donates a proton to another Accepts a proton from another
substance substance
Acid and Base strength
Not all acids and base have to same strength. In the context of chemistry, stronger acids have a stronger
ability to donate hydrogen atoms to other molecules. In other words, they completely dissociate in water.
On the other hand, stronger bases have a stronger ability to accept those hydrogen atoms. One interesting
point is that strong acids have weak conjugate bases and strong bases have weak conjugate acids visa versa.
The relationship is presented in the table below
The reactions that involve proton transfer all deal with the strength of two bases to attract protons.
H A + H 2O ↔ H 3O + A
In the reaction above, if H2O is the stronger base, it is likely that it will receive the proton from HA
producing H3O+.
Autoionization of Water
Even though water looks like an unreactive liquid it constantly undergoes ionization and deionization. What
that means is water molecules are constantly donating protons to other water molecules and becoming acids
and bases. But this proton transfer is so rapid that water molecules stay ionized for a very short time. When
we derive an equilibrium constant for the ionization of water we get an expression called ion-product constant:
Kc = [H3O+][OH-]
As I mentioned, since the ionization is so rapid and seldom the constant is very small. At 25 ° C it equals
about 1.0 × 10-14. And when concentrations of H3O+ and OH- are equal, we call that a neutral solution. This
constant is very important for the chemistry exams because it helps solve many pH calculations.
pH
Concentration of H+ is usually very small. So it is better to represent it as whole numbers. To do that,
scientists set up a pH scale. pH is basically the negative log of the concentration of H+
pH = -log[H+]
For example when a solution has an H+ concentration of 1.0 × 10-7, the pH would be -log[1.0 × 10-7] or 7.
pH Scale
The pH scale consists of pH’s 1-14. 1 is very acidic and 14 is very basic and 7 is neutral. As numbers from
one to six get closer to seven, it becomes less acidic. As numbers from seven to fourteen get closer to seven,
it becomes less basic. By looking t the scale below, you can see that acidic substances have higher
concentrations and basic substances have higher hydroxide concentrations.
pOH Scale
Instead of using H+ concentration, pOH uses the concentration of OH-. So pOH would also be the
-log[OH-]. One important formula to remember for the AP Exam is:
pH + pOH = 14
This equations helps a lot in making pH calculations during the AP Chemistry exam.
Strong Acids and Bases
Now it is time to see how the concept of pH relates to acid and base concentration. It is easy to start off
with strong acids and bases because they completely ionize in water. So for acids, the concentration of the
acid equals the concentration of H+ because the acid completely dissociates. Same for bases.
For example, what would be the pH of the solution that contains 1.0 × 10^-4 M of HCl? Since HCL is a
strong acid, it would completely dissociate. Hence the concentration of HCl would equal H+.
So pH = -log[1.0 × 10-4]= 4
The Acid Dissociation Constant
The AP test also requires you to know the concept of the Acid dissociation constant. The Acid dissociation
constant is a quantitative measure of the strength of an acid in a solution. The symbol for it is Ka. The K
part allows us to know that this is a equilibrium constant between the concentration of Hydronium ion to
the concentration to its conjugate base.
To see this take a look at the reaction,
H A + H 2 O ⇔ A− + H 3 O
Now we can create a equilibrium constant between the species, keeping the product on the numerator and
the reactants on the denominator.
[A− ][H O]
K a = [HA][H3 O]
2
But, we can take out the concentration of water, as water is seen in all acid reactions, it can simply just bee
seen as a constant that is kept the same for all reactions. And because of that we can rewrite the reaction,
[A− ][H 3 O]
Ka = [HA
We normally use the pKa, or the logarithmic scale of Ka when we want to discuss the strength of an acid.
The more positive the value of pKa is, the stronger the acid is.
In the exam, the Ka value equation is given in the formula sheet at the start of the exam, so it is not required
to memorize the complete reaction formula.
The Base Dissociation Constant
Similar to the concept of Ka(Acid dissociation constant), we can create a similar thing using bases instead of
acids. This is called the base dissociation constant. The symbol for it is Kb. Again, the K part allows us to
know that this is an equilibrium constant between the concentration of the Hydroxide, to the concentration
to its conjugate acid.
To see this take a look at the reaction,
AOH + H 2 O ⇔ A− + OH
Again we can create an equilibrium between the species
[A− ][OH]
K b = [AOH][H
2 O]
Again, we can take out the concentration of water due to it being a constant across multiple reactions.
−
K b = [A[AOH]
][OH]
We again normally use the pKb, or the logarithmic scale of Kb when we discuss the strength of a base. The
more positive pKb value, the stronger the base is.
In the exame the formula for Kb is stated.
*We can now relate pKw, pKa, and pKb
If we multiply pKa and pKb we would result in the pKw value of 10-14 as that is the water dissociation
constant
pKw = pKa × pKb
SAMPLE QUESTIONS
1. The pKa of the 0.1M solution with the lowest hydroxide concentration is
a) 3.3
b) 6.7
c) 8.6
d) 9.3
2. If a solution has a hydronium concentration of 2.0 * 10-6, what is its hydroxide ion concentration and the
acidity of the solution
a) 5 * 10-9, Acidic
b) 5 * 10-8, Basic
c) 1.2 * 10-6, Acidic
d) 1.2 * 10-5, Basic
3. Which of the following salt solutions would have the highest pH?
Compound Ka/Kb
3. b), A basic anion will drive the pH value up because they are conjugate bases of a weak acid. If the Ka of
the weak acid of the conjugate base is greater than the Kb of the weak base of the conjugate acid, the
solution will be basic.
4. b), The ion C2H3O2- and its conjugate acid HC2H3O2 will form a buffer. Because neither the acid or the
base are strong, they will not ionize completely in solution, this will ensure that there will be some of the
solution causing a buffer to form
5. b), (0.100 mol NaoH)/(1L NaOH) * (1 mol H2A)/(2 mol NaOH) = 2.5 * 10-4 mol H2A
With the moles of diprotic acid, the molar concentration can be calculated:
M=(2.5*10-4 mol H2A)/(0.025L)= 0.010M H2A
6. c), the first step is to use a strong acid like HCl and a strong base like KOH to get the moles of the acid.
(0.50L)(1.0M) = 0.50 moles of acid. (0.30L)(2.0M) = 0.60 moles of base
Since there are 0.10 extra moles of base, this causes the solution to be very basic
7. a), a buffer contains a weak acid or a base and its conjugate. The most effective buffer of all of these, will
be the one that has the highest concentration of each. The Ka value does not affect the effectiveness of the
buffer.
8. a), in this neutralization, HCl reacts with NaOH
Chapter 15: Chemical Equilibrium
THE CONCEPT OF EQUILIBRIUM
“To be in equilibrium means to be in a state of balance.”
At dynamic equilibrium, the rate at which the reactants turn into the products is equal to the rate at which
the products turn into the reactants. Static equilibrium occurs when all the particles are at rest, so there is no
movement between the reactants and products.
The concentrations of the reactants and products depend on the initial concentration of the reactants.
Mixtures can have different concentrations if the initial concentrations are different. However, they all
follow the law of equilibrium concentration, or the law of mass action, which states that “all of the products
multiplied together, divided by the concentrations of all reactants multiplied together,” equals the
equilibrium constant, K.
A general reaction looks like: aA + bB ↔ cC + dD and the equilibrium expression looks like:
c
[D]d
Kc = [C]
[A]a [B]b
. The subscript c on the K expresses the concentration in molarity units when calculating the
constant.
Three important points have to be kept in mind:
1) The equilibrium constant of an equation that is in the reverse direction is the reciprocal of the
equilibrium constant in the forward direction:
A + B ↔ C + D K1
C + D ↔ A + B 1/K1
2
For example, for 2NO2(g) ↔ 2NO(g) + O2(g), K = [N[NO]O2] [O2]
2 , and for (2NO(g) + O2(g) ↔
2
2NO2(g)), K 1 = [N[NO]O2]
2
[O2]
.
2) If a reaction is multiplied by a number, the equilibrium constant is equal to the original equilibrium
constant raised to a power equal to that number.
A+B ↔ C+D K1
nA + nB ↔ nC + nD K = K1n
For example,
N2O4 (g) ↔ 2NO2(g) Kc = 0.212
2N2O4 (g) ↔ 4NO2(g) Kc = 0.2122 (at 100°C).
3) The equilibrium constant of two or more reaction is the product of the equilibrium constants for
each of the reactions:
A + B ↔ C + D K1
C + F ↔ G + A K2
_____________________________
B + F ↔ D + G (K1)(K2)
2
For example, for 2NOBr(g) ↔ 2NO(g) + Br2(g) Kc = [N[NO]OBr]
[Br2]
2 = 0.014
2
[BrCl]
Br2(g) + Cl2(g) ↔ 2NO(g) + 2BrCl(g) Kc = [Br = 7.2,
2 ][Cl2 ]
the net sum of these equations is: 2NOBr(g) + Cl2(g) ↔ 2NO(g) + 2BrCl(g).
Kc3 = (0.014)(7.1) = 0.10.
To summarize key points about equilibrium:
● At equilibrium, the concentrations of the reactants and products do not change regardless of time.
● Reactants and products cannot escape from the system in order to reach equilibrium.
● At equilibrium, the ratio of the concentrations equals the constant, K.
THE EQUILIBRIUM CONSTANT
d
[E]e
As mentioned in the previous section, the equilibrium expression is obtained by KC = [D][A]a [B]b
.
An important point to keep in mind is that the equilibrium expression depends only on the stoichiometry of
the reaction, not on its mechanism.
According to the law of mass action, the numerator of the constant Kc is “the product of the concentrations
of all substances on the product side of the equilibrium equation, each raised to a power equal to a power
equal to its coefficient in the balanced equation,” and the denominator is derived in a similar way. The value
of Kc depends only on the particular reaction and on the temperature, not on the initial quantity of
reactants and products.
For example,
EQUILIBRIUM CONSTANTS IN TERMS OF PRESSURE, Kp
When the reactants and products are gases, the equilibrium expression can be denoted in terms of partial
D)d (P E)e
pressures: Kp = (P
(P A)a (P B)b
, where the subscript stands for pressure, PA is the partial pressure of A in
atmospheres, PB is the partial pressure of B in atmospheres, and so on.
For a given reaction, the value of Kc are usually different. Therefore, it is important to label the K with a
subscript. In a gas-phase reaction, the equilibrium constant can be either written as Kp or Kc. Kc.The
relationship between these two constants can be expressed as K p = K c(RT )Δn . In this equation, R is the gas
law constant ( 0.0821 L atm mol−1 K −1 ) , T is the temperature in Kelvin, and Δn is the change in the
number of moles of gas.
Δn = moles of gaseous product − moles of gaseous reactant .
For (NH4)2CO3(s) → 2NH3(g) + CO2(g) + H2O(g), the Δn is (2 + 1 + 1) - 0 = 4 moles.
If the value of Kc for the following reaction: N2 (g) + 3H2 (g) ↔ 2NH3 (g)
is 9.60 at 300°C, theKp for this reaction at this temperature can be calculated by
(9.60)
K p = K c(RT )Δn = (9.60)(0.08206 × 537)−2 = (0.08206 ×537)2
= 4.34 × 10−3 , where
Δn = 2 − 4 = − 2 and the temperature is 273 + 300 = 537 K.
MORE INTO EQUILIBRIUM CONSTANTS
If K >> 1, the reaction is product-favored, so the product
predominates and there are more products than reactants. On the
other hand, if K << 1, the reaction is reactant-favored,,and the
reactants are favored and and there are more reactants than
products.
HETEROGENEOUS EQUILIBRIA
A homogeneous equilibria occurs when the substances in the
reactant and product sides are all in the same phase. This is more
common than heterogeneous equilibria, where the substances in
the equilibrium are in different phases. Generally, the
concentration of a pure solid or pure liquid is not included in the equilibrium-constant expression. This can
be explained in two ways:
1) When the mass of a solid is doubled, its volume also doubles. The concentration, which is the ratio
of mass to volume, does not change.
2) The equilibrium constants of a thermodynamic reaction is defined in terms of activities, rather than
concentrations or partial pressures. That means that the activity of substances in an ideal mixture is
the ratio of the concentration or pressure of the substances to a reference concentration or pressure.
For a pure substance, the reference value is the concentration of the pure substance, so the activity is
always 1.
For example, the equilibrium constant expression for CO2(g) + H2(g) ↔ CO(g) + H2O(l) is
Kc = [CO[CO] . H2O does not appear in the expression because it is a liquid.
2 ][H 2 ]
THE REACTION QUOTIENT AND PREDICTING THE DIRECTION OF A REACTION
The equilibrium constant K is a value that is obtained when a reaction is at equilibrium. When a reaction is
not at equilibrium, the reaction quotient, Q, is used.
c
[D]d [C]c [D]d
Kc = [C] a
[A] [B] b at equilibrium Q = [A]a [B]b
either at or not at equilibrium
There are 4 principles regarding the relationship between Qc and Kc or Qp or Kp.
1) If Q does not change with time, Q = K, and the reaction is at equilibrium.
2) If Q < K, the concentration of the products is greater than that of the reactants. The reaction
reaches equilibrium by forming more products, moving from left to right.
3) If Q > Kc, the concentration of the reactants is greater than that of the products. The reaction
attains equilibrium by forming more reactants, moving from right to left.
For example, at 448°C, the equilibrium constant Kc for the reaction H2(g) + I2(g) ↔ 2HI(g) is 50.5. If we
start with 2.0 × 10−2 mol of HI, 1.0 × 10−2 mol of H2, and 3.0 × 10−2 mol of I2 in a 2.00-L container, we
can predict the direction of the reaction:
2 (1.0×10−2 )2
The reaction quotient is: Qc = [H[HI] = (5.0×10−3 )(1.5×10−2 )
= 1.3. Since Qc < Kc, the reaction should move
2 ][I 2 ]
from left to right. The concentration of H2 and I2 must decrease and the concentration of HI must increase
to achieve equilibrium.
Chemists often need to calculate the quantity of reactants and products in a reaction at equilibrium.
However, to do that, they use the known equilibrium-constant expression to find the unknown quantity.
For instance, for N2(g) + 3H2(g) ↔ 2NH3(g), Kp = 1.45 × 10−5 , at 500°C. In an equilibrium mixture of
the three gases at 500°C, the partial pressure of H2 is 0.928 atm and that of N2 is 0.432 atm. The partial
pressure of NH3 in this equilibrium mixture is:
(P N H3)2 x2
Kp = P N 2 (P H 2 )3
= (0.432)(0.928)3
= 1.45 × 10−5
x2 = (1.45 x 10−5 )(0.432)(0.928)3 = 5.01 × 10−6
x = √5.01 × 10−6 = 2.24 × 10−3 atm = PNH3
LE CHÂTELIER’S PRINCIPLE
In 1888, French chemist Henry Le Châtelier observed that reactions react until they reach equilibrium. If an
external force disturbs the equilibrium, the chemicals react until equilibrium is attained.
Chemical changes occur when one or more of the products or reactants are removed or added. Physical
changes include changes in temperature, pressure, and volume. Understanding these changes allow chemists
to maximize products and minimize waste.
Effect of Concentration
Chemical reactions aim to achieve equilibrium. When the concentrations of the reactant or product is
altered, the system shifts until it is in a state of balance. If a chemical system is at equilibrium and the
concentration of either the reactant or the product decreases, the system reacts by consuming more of that
substance. Conversely, if the concentration of either the reactant or the product increases, the system
produces more of the substance that is needed.
If more is added to the reactant, the system reacts by shifting to toward the product (producing a greater
amount of product and reducing the amount of reactant). If more is added to the product, the reaction
shifts towards the reactants. If reactants are moved, the system shifts the reaction towards the reactants,
producing more products and reducing reactants. If reactants are added, the system shifts towards the
products.
Effect of Pressure and Volume
Increasing pressure affects gases, but it does not have much effect on solids and liquids. Increasing the
pressure of a gaseous reaction by decreasing its volume will affect the equilibrium only if Δn is not zero. If
Δn = 0 , there is no effect because the number of moles of the reactants is equal to the number of moles
of the products. In general, in a reaction, the side the with fewer gas molecules is favored. When Δn > 0 ,
the reaction will shift to the left because there the number of moles of gas of the reactants is less than that
of the products. These effects can be summarized in the following table:
Value of Δn Increasing Pressure Lowering Pressure
1.
Analyze the equilibrium mixture above. Which K value correctly describes this mixture at equilibrium?
(a) K = 0
(b) K = 1
(c)K > 1
(d)K < 1
2. Calcium fluoride dissociates in water as follows:
C aF 2 (s) ↔ Ca2+ (aq) + 2F − (aq) K sp = 3.45 × 10−11
(a) 3.45 × 10−11
(b) − 3.45 × 10−11
(c) 2.90 × 1010
(d) − 2.90 × 1010
3. Consider the hypothetical reaction shown by the following balanced equation.
2A + B ↔ C + 2D
All species are gases. The value of Kp is 2.0. In a particular reaction mixture, the partial pressures are: PA =
1.0 atm, PB = 2.0 atm, and Pc = 2.0 atm, and PD = 1.0 atm.
Which of the following statements is CORRECT concerning this system?
(a) The system is at equilibrium.
(b) The system will shift to the left.
(c) The system will shift to the right.
(d) A value of 2.0 for Kp means that the number of product molecules present at equilibrium will
be twice the number of reactant molecules in the system.
4. Consider the following reactions:
H2O(g) + CO(g) ↔ H2(g) + CO2(g) Kc = X
3FeO(s) + 3CO(g) ↔ 3Fe(s) + 3CO2(g) Kc = Y
2H2O(g) ↔ O2(g) + 2H2(g) Kc = Z
Which of the following is the Kc for the reaction below?
Fe(s) + H2O(g) ↔ FeO(s) + H2(g)
(A) X + Y3 + √Z
(B) X + Y3
1
(C) X ( Y1 ) 3
(D) √Z1
(Y 3 )
5. Consider the following reaction:
CH4(g) + 2H2S(g) ↔ CS2(g) + 4H2(g)
1.00 atm CH4, 1.00 atm CS2, 2.00 atm H2S, and 2.00 atm H2 are mixed in a vessel at 960°C. At this
temperature, the reaction will take more methane and hydrogen sulfide gases. Which of the following is a
possible K for this reaction?
(A) K = 16
(B) K = 8
(C) K = 4
(D) K = 1
6. For this reaction N2O4 (g) ↔ 2NO2(g), a reaction mixture initially contains both substances at STP. If Kp
= 1.5 at this temperature, which of the following statements is true before any reaction occurs?
(A) The reaction is at equilibrium.
(B) The reaction will proceed to the right.
(C) The reaction will proceed to the left.
(D) The initial reaction mixture will remain unchanged when the reaction occurs.
7. Consider the following reaction:
2SO2(g) + O2(g) ↔ 2SO3(g)
… with concentrations of:
● SO2(g) = 0.2 M
● O2(g) = 0.5 M
● SO3(g) = 0.7 M
… at equilibrium for a given temperature.
If the same reaction was completed using different concentrations:
● SO2(g) = 0.1 M
● O2(g) = 0.3 M
● SO3(g) = 0.5 M
… which of the following would occur?
(A) K > Q The reaction will shift left.
(B) K < Q The reaction will shift left.
(C) K > Q The reaction will shift right.
(D) K < Q The reaction will shift right.
8. Consider the following data:
Experiment K
1 5
2 10
3 0.2
4 25
During one of the experiments: A + B ↔ C
…. Where [A] = [B] = [C] = 0.20 M at equilibrium. Which of the following experiments represents K for
2A + 2B ↔ 2C?
(A) 1
(B) 2
(C) 3
(D) 4
9. In the reaction
2HI(g) ↔ H2(g) + I2(g)
the equilibrium constant is 0.020. If 0.200 mol of HI is placed in a 10.0-L flask, how many moles of I2(g)
will be in the flask when equilibrium is reached?
(A) 0.0022
(B) 0.025
(C) 0.022
(D) 2.2
10. Additional Cl2(g) is injected into the system at equilibrium. Which of the following graphs best shows
the rate of the reverse reaction as a function of time? (Assume that the time for injection and mixing of the
additional Cl2(g) is negligible.)
FRQ
The synthesis of ammonia (NH3NH3) during the Haber Process can be represented by the following
chemical equation:
b. Find the equilibrium partial pressure of ammonia gas at 500°C if the equilibrium mixture contains 0.25
atm of nitrogen gas and 0.75 atm of hydrogen gas.
c. If the volume of the container is reduced to 0.50 L, will the rate of the forward reaction that produced
ammonia increase, decrease, or remain the same? Justify.
Initial 0.0200 M 0 M 0 M
Concentration
Answer
[H 2 ][I]2 (x)(x) x2
[HI]2
= 0.020 = (0.0200−2x)2
= (0.0200−2x)2
x2
√020 =
√ (0.0200−2x)2
x
0.1414 = 0.0200−2x
(0.1414)(0.0200-2x) = x
0.002828 - 0.2828x = x
0.002828 = 1.2828x
x = 2.2 × 10−3
10. The correct answer is Choice B. Choice A does not work because there should some Cl2 in the system
before the additional Cl2 is injected. Choice C cannot be the answer because with the addition of Cl2, the
reverse rate should be higher than the rate at equilibrium. The reverse rate should increase immediately and
then level off with the addition of Cl2, so B, not D is the answer.