Chemistry 103

27.1-27.2, 27.
4
Monday, March 29, 2010
8:05 AM
• Chemical structure of living matter

○ Cell
 The fundamental unit of life
○ Elements
 Trace quantities required by all
□ Vanadium
□ Chromium
□ Manganese
□ Iron
□ Cobalt
□ Nickel Copper Zinc
□ Molybdenum
□ Boron
□ Fluorine
□ Silicon
□ Selenium
□ Iodine
 Trace quantities required by some (MAYBE)
□ Tungsten
□ Tin
□ Arsenic
□ Bromine
 Fundamental elements
□ Hydrogen
□ Carbon
□ Nitrogen
□ Oxygen
□ Sodium
□ Magnesium
□ Phosphorus
□ Sulfur
□ Chlorine
□ Potassium
□ Calcium
○ Lipids
 Substances that make up plant and animal tissue
□ Are soluble in low-polarity solvents
□ Triglycerides
 Esters of glycerol and long-chain monocarboxylic acids
◊ Ester
► A compound that comes from a reaction of an oxoacid and a
hydroxyl group (like an alcohol)
 Glycerol provides the backbone
 Fatty acids provide -acyl groups
□ Soaps
 Glycerols and salts of fatty acids
 Saponification
◊ Process of hydrolyzing a triglyceride in an alkaline solution
Fats
Chemistry 103 Page 1

□ Fats
 Glyceryl esters with saturated fatty acid components
 Solid at room temperature
□ Oils
 Glyceryl esters with unsaturated fatty acid components
 Liquid at room temperature
 Hydrogenation
◊ Catalytic addition of hydrogen
► Oils/low melting fats are turned into higher melting fats
□ Phospholipids
 Glycerol, fatty acids, phosphoric acid, and a nitrogen base
 Hydrophilic head
◊ Solubilize and transport fats and oils in an aqueous medium
○ Proteins
 Amino acid
□ A carboxylic acid that contains an amine group
 Colorless and crystalline
 High melting point
□ Essential amino acids
 Cannot be produced by the body
◊ Must come from food
□ Alpha amino acid
 Has the amino group on the alpha carbon
□ In a strongly acidic solution, the amino acid exists as a cation
 A proton from the solution attaches to the N in the amino group
◊ Form NH3+
□ In a strongly basic solution, the amino acid forms through the loss of protons
 The COOH group and NH3+ group lose protons
◊ Zwitterion
► A dipolar ion
□ Isoelectronic point
 The pH at which the dipolar structure predominates
 Peptides
□ Peptide bonds
 The bond between two amino acids
◊ Formed by a dehydration reaction (removal of water)
◊ Polypeptide
► The joining of a lot of amino acids
 Proteins
□ A large polypeptide with a molecular mass of over 10,000u
□ Denaturation
 Profound changes caused by heat, salts, or UV radiation
◊ Causes proteins to lose biological activity
□ Structure
 Primary structure
◊ Exact sequence of amino acids
 Secondary structure
◊ The shape of the chain of amino acids
 Tertiary structure
◊ The initial winding of the chain into a geometric shape
 Quaternary structure
◊ The arrangement of the shapes into a larger protein

26.1
10:17 AM
• Isomerism
○ Isomers
 Compounds that have the same molecular formula but different structural formulas
○ Skeletal isomerism
 The structural skeletons of the isomers differ
○ Positional isomerism
 Differ in the position of a side chain
• Functional groups
○ Ethane
 C2H6
○ See table on p. 1080
○ Ester
○ Ketone
○ Ether
○ Alcohols
 Usually basic
 Primary alcohol
 Secondary alcohol
○ Amine
• Nomenclature
○ Hydrocarbons
 Saturated
□ Alkanes
○ Naming
 Rules
1. Select the longest continuous carbon chain in the molecule and use the hydrocarbon name
of this chain as the base name
2. Consider every branch of the main chain to be something derived from another
hydrocarbon
3. Number the C atoms of the base chain so that the side chains appear at the lowest numbers
of C atoms
4. Name each side chain according to its chemical identity and the number of the C atom (di,
tri, tetra, etc.) and write the appropriate carbon number
5. Separate numbers from one another by commas and from letters by hyphens
6. List the side chains alphabetically

16.1-16.5
10:17 AM
• Arrhenius Theory
○ In aqueous solutions strong electrolytes exist only in the form of ions
 Weak electrolytes exist both as ions and as molecules
○ Neutralization reaction
 The combination of hydrogen ions and hydroxide ions into water
○ Shortcomings
 Does not recognize the role of a solvent in ionization
 Does not account for amphiprotic substances
• Bronsted-Lowry Theory
○ Acid
 Proton donor
 Conjugate acid
□ A base that has accepted a proton
○ Base
 Proton acceptor
 Conjugate base
□ An acid that has donated a proton
○ Amphiprotic
 A substance that can act as either an acid or a base
○ Base Ionization constant
 The equilibrium constant expression for an acid/base equation that does not include the
H20 concentration
□ Kb = [A+][B-]/[Initial]
○ Acid ionization constant
 Ka = [A-][H3O+]/[HA]
○ In an acid-base reaction, the favored direction or a reaction is from the stronger to the weaker
member of an acid-base pair
• pH
○ Self-ionization of water
 For each H20 molecule that acts as an acid, another acts as a base
○ Kw
 Kw at 25C = [H3O+][OH-] = 1.0 *10^-14
 pKw = pH + pOH = 14.00
○ pH = -log[H+]
• Strong/Weak Acids and Bases

○ Weak acids are the ones not in the list of strong acids
○ Weak bases are usually an ammonia molecule combined with an organic group
○ Percent ionization
 % = [H3O+ from HA]/[HA initial]
○ Ka * Kb = Kw
 K(a) is an acid or conjugate acid
 K(b) is a base or conjugate base

Lecture 1
10:18 AM
Formulas & Theorems Covered Today: Homework:

Ch 26: 18, 21, 22
Ch 27: 1, 3, 27, 29
Ch 16: 1, 2, 3, 10, 11, 17, 23, 25, 27
Lecture Topic:
During the lecture, take notes here.
• Essential elements
• Chemical structure of living matter
○ Cell
 The fundamental unit of life
○ Elements
 Trace quantities required by all
□ Vanadium
□ Chromium
□ Manganese
□ Iron
□ Cobalt
□ Nickel Copper Zinc
□ Molybdenum
□ Boron
□ Fluorine
□ Silicon
□ Selenium
□ Iodine
 Trace quantities required by some (MAYBE)
□ Tungsten
□ Tin
□ Arsenic
□ Bromine
 Fundamental elements
□ Hydrogen
 25% by weight
□ Carbon
 9.5%
□ Nitrogen
 1.4%
□ Oxygen
 63%
□ Sodium
 Cells don't like this so it is in small quantities
□ Magnesium
□ Phosphorus
 1%
□ Sulfur
□ Chlorine
□ Potassium
□ Calcium
Properties of these elements that make life so dependent on them

 Properties of these elements that make life so dependent on them
□ Abundant in the crust
□ Form covalent bonds
 By electron pair sharing
◊ Allows for dipoles/other charges
► Through sharing, there is a directionality and a shape
– The shape allows it to have different functions
– Which hydrogen ions can come off?
 Which would cause changes in the functionality?
 Functional groups
□
○ Lipids
 Substances that make up plant and animal tissue
□ Are soluble in low-polarity solvents
□ Triglycerides
 Esters of glycerol and long-chain monocarboxylic acids
◊ Ester
► A compound that comes from a reaction of an oxoacid and a hydroxyl
group (like an alcohol)

Lecture 2
Tuesday, March 30, 2010
10:00 AM
Lecture Topic:
• Lipids
○ Define chemically unique spaces in living systems
 Lipid bilayers
□ Cells and cell compartments
 Define specialized compartments that separate reactants
□ Polar (hydrophilic) head with a nonpolar (hydrophobic) tail
 Tail is hydrophobic because it consists of carbon and hydrogen in covalent bonds
• Acids and bases
○ Arrhenius
 Base
□ Dissociates into OH- ions
 Acid
□ Dissociates into H+ ions
 K(25 degrees C) = [H30+] x [OH-] = 1.00 * 10^-14
□ [] --> concentration
□ The forward reaction (H20 + H20 <--> H30+ + OH-) is not favored
 pH
□ pH = -log([H+])
 Ranges from 0 to 14
 K = 1 * 10^-14 = [H+][OH-] = [H30+][OH-]
◊ 14 = pH + pOH
 Sig figs only matter after the decimal point
◊ Start counting only after the decimal
□ Things that shift pH
 Dissolved gases
 Conjugate acids/bases
□ Conjugate Base
 Everything that is left of an acid molecule after a proton (H+) is lost
□ Conjugate Acid
 Everything that is left of a base molecule after a proton (H+) is gained
 Strength
□ Strong Acid
 Equilibrium position is far to the right
 Completely dissociates
 Yields a weak conjugate base
◊ Spectators
List

 List
◊ Perchloric acid
◊ Sulfuric acid
◊ Nitric acid
◊ Hydroiodic acid
◊ Hydrobromic acid
◊ Hydrochloric acid
□ Weak acid
 Does not completely dissociate
 Equilibrium position is far to the left
 Conjugate base is MUCH stronger
 Smaller Ka values
□ Strong base
 Small Ka values
 Equilibrium is to the left

Lecture 3
Wednesday, March 31, 2010
10:00 AM

Rest of chapter 16, 17.1-17.4
Ch 16: 31, 33, 39, 47, 51, 55, 60, 62, 65,
74, 75, 85, 112
Ch 17: 3, 7, 9, 16, 23, 25
Lecture Topic:
• Amino acid
○ Alpha amino acid
 Has both a basic part and an acidic part
□ An ammonium group and a carboxylic acid
 Can be either weak or strong depending on protonation state
◊ Whether a proton has been added or removed
○ Peptide bond formation and hydrolysis
 Directionality of bond
□ Information is read from the amino term to the carboxyl term
 The other way does not mean the same thing
 Hydrolysis
□ Reaction that breaks down a peptide bond
• Acids and bases
○ Ka
 Ka is large
□ Strong acid
□ Equilibrium constant is to the right
□ [H+] = [acid]
□ Conjugate base is much weaker
□ pK(a) is small
 Ka is small
□ Weak acid
□ Equilibrium is to the left
□ [H+] <<<<< [acid]
□ Conjugate base is much stronger
□ pK(a) is large
 Ka = [A-][H30+]/[HA]
 pKa = -log(Ka)
○ Kb
 Use when
 A-(aq) + H2O --> OH-(aq) + HA(aq)
○ Weak acids and bases
 Ionization percent (dissociation)
□ % = [H30+ (from HA)]/[HA(initial)]
 For weak acids, % decreases as initial concentration increases
 For strong acids, % = 100 (always)
○ pH
 Ka > Kb
pH < 7

□ pH < 7
 Ka < Kb
□ pH > 7
 Ka = Kb
□ pH = 7

16.6-16.9
Saturday, April 03, 2010
11:07 AM
• Polyprotic acids
○ Acids that have more than one H+ ion to donate
 Steps
□ Ionization is complete in the first step
 So X M of an acid gives X M of H3O+ as well as X M of the conjugate base
□ As many H+ ions as the ion has can be removed in SUCCESSIVE reactions
 Not all in one
◊ ONLY ONE H+CAN BE REMOVED PER REACTION
 pK(a) increases as H+ ions are removed
□ K(a) decreases as H+ ions are removed
 The most H3O+ ions are formed in the first reaction
○ Trends
 As reactions progress, the acid goes from weaker to stronger
○ Exceptions
 H2SO4
□ Starts out strong and gets weaker
○ Steps
1. Identify species present
2. Write equations that include these species
1) Equilibrium constant expression
2) Material balance equation
3) Electroneutrality condition
3. Solve system for unknowns
• Ions as acids or bases

○ pH of salt solutions
 Hydrolysis
□ The reaction between an ion and water that results in the splitting of water
 Strong acid + strong base
□ Salts do not hydrolyze water
□ pH = 7
 Weak acid + strong base
□ Salts hydrolyze water
□ pH > 7
□ The anion acts as a base
 Weak base + strong acid
□ pH < 7
□ The cation acts as an acid
 Weak acid + weak base
□ pH depends on Ka and Kb
 Ka * Kb = Kw
• Molecular structure and acid-base behavior

○ Strength of binary acids
 The stronger the X-H bond, the weaker the acid
□ Depends on electronegativity
Greater electronegativity difference

 Greater electronegativity difference
◊ Easier electron loss
◊ Greater polarity
 Bond length and energies
□ HI
 160.9 pm
 297 kJ/mol
□ HBr
 141.4 pm
 368 kJ/mol
□ HCl
 127.4 pm
 431 kJ/mol
□ HF
 91.7 pm
 569 kJ/mol
○ Strength of oxoacids
 The strength depends on the attractions on electrons from the O-H bond
□ Electronegativity
 The higher the electronegativity of an element, the more acidic the oxoacid
○ Strength of organic acids
○ Strength of amines as bases
 If an H in an amine group is replaced with an element more electronegative than H, the base
becomes weaker
 Aromatic rings reduce the strength of a base
• Lewis acids and bases

○ Lewis acid
 A substance that is an electron pair acceptor
 Have vacant orbitals that can accommodate electron pairs
○ Lewis base
 An electron pair donor
 Have lone pairs available for sharing
○ Adduct
 Product of a Lewis acid-base reaction
 B: + A --> B:A
○ Formation of complex ions
 Polyatomic ions with a central metal ion
□ Form hydrated metal ions in aqueous solutions because the water acts as a Lewis base
and the metal ion acts as a Lewis acid

17.1-17.4
5:01 PM
• Acid-base equilibrium
○ Solutions of weak and strong acids
 Common-ion effect
□ Suppression of the ionization of a weak electrolyte caused by adding more of an ion
that is a product of this ionization
 Usually in the form of adding a strong acid that immediately dissociates to form
H3O+ or OH- and changing the equilibrium
○ Solutions of weak acids and their salts
 The salt of a weak acid is a strong electrolyte
□ It completely dissociates in water
 Common-ion effect
□ The anion is the ion that is used in the common ion effect
○ Solutions of weak bases and their salts
 Same as a weak acid EXCEPT the cation is used in the common ion effect
• Buffer solutions
○ Buffer solutions
 Solutions whose pH values change only very slightly on the addition of small amounts of acid
or base
 Weak acid + conjugate base
 Weak base + conjugate acid
○ Addition of a buffer and its effects
 Adding acidic buffer
□ Increases concentration of an acidic solution
 Adding a basic buffer
□ Increases concentration of the basic solution
 pH = pKa + log([conjugate base]/[acid])
□ .1 < log[conjugate base]/[acid] < 10
□ The molarity of each buffer component exceeds the value of Ka by a factor of at least
100
○ Calculating pH changes
 Weak acid
□ Titrate with NaOH
 HA + OH- --> A- + H2O
 [H3O+] = Ka([HA]/[A-])
 Weak acid and salt
□ pH = Ka([HA]/[A-])
 Salt of weak acid
□ Titrate with HCl
 A - + H+ --> HA
◊ [H3O+] = Ka([HA]/[A-])
 Weak base
□ Titrate with HCL
 B + H+ --> BH+
 [H3O+] = Ka([BH+]/[B]) = (Kw/Kb)([BH+]/[B])
 Weak base and salt
□ [H3O+] = Ka([BH+]/[B]) = (Kw/Kb)([BH+]/[B])
 Salt of weak base
Titrate with NaOH

□ Titrate with NaOH
 BH+ + OH- --> B + H2O
 [H3O+] = Ka([BH+]/[B]) = (Kw/Kb)([BH+]/[B])
○ Buffer capacity and range
 Buffer capacity
□ The amount of acid or base that a bugger can neutralize before its pH changes
□ When the concentrations of a weak acid and its conjugate base are LARGE and EQUAL
 Buffer range
□ The pH range over which a buffer effectively neutralizes added acids and bases and
maintains a fairly constant pH
• Acid-base indicators
○ Substance whose color depends on the pH
 pH = pK(Hin) + log([In-]/[HIn])
□ If 90% of the indicator is in the form HIn, the solution will take on the acidic color
□ If 90% of the indicator is in the form In- the solution will take on the basic color
• Neutralization reactions and titration curves

○ Neutralization reaction
 Equivalence point
□ The point at which both acid an base have been consumed and NEITHER is in excess
 Titrant
□ The base used in a titration
 In a buret
 End point
□ The point at which the indicator changes color
□ Matches the equivalence point
 Titration curve
□ Graph of pH vs. volume of titrant
○ Millimole
 1* 10^-3 mole
○ Titrations
 Strong acid + strong base
□ pH has a low value at the beginning of the titration
□ pH changes slowly until just before the equivalence point
□ At the equivalence point, the pH rises very sharply
□ Beyond the equivalence point, the pH rises very slowly
□ Indicator
 Any indicator that changes in between 4 < pH < 10
 Weak acid + strong base
□ Steps
1. Stoichiometry first
i) Find what's left
ii) Reaction runs to completion, find remaining species
2. Equilibrium
i) Determine position of weak acid equilibrium
3. Use
i) Ka in the weak acid range
ii) Use pH
1. Initial pH is high (less acidic) than it is in the titration of a strong acid

2. The initial increase in pH is sharp
a) Common ion effect from the weak acid
3. The pH then only changes gradually
4. At the point of half-neutralization, pH = pKa

3. The pH then only changes gradually
4. At the point of half-neutralization, pH = pKa
5. At the equivalence point, pH > 7
a) The conjugate base hydrolyzes and produces OH-
6. Beyond the equivalence point, the curve looks like the curve for a strong acid
a) The dominant species is A-
7. The steep portion is over a short range (pH 7 to pH 10)
8. Indicator
a) The indicator must change colors above pH 7
 Weak base + strong acid
1. At the equivalence point, pH < 7
2. The curve has a negative slope
3. At the equivalence point, the pH rises sharply
4. After the equivalence point, the curves become dependent (and become the same
curve)
 Weak polyprotic acid
□ Separate equivalence points for each acidic hydrogen

Lecture 4
Monday, April 05, 2010
1:45 PM
Lecture Topic:
 Proteins
□ A large polypeptide with a molecular mass of over 10,000u
□ Denaturation
 Profound changes caused by heat, salts, or UV radiation
◊ Causes proteins to lose biological activity
□ Structure
 Primary structure
◊ Exact sequence of amino acids
 Secondary structure
◊ The shape of the chain of amino acids
 Tertiary structure
◊ The initial winding of the chain into a geometric shape
◊ Stabilized by side chains
 α-Amino acid
◊ The weak acid or base function depends on the side change
◊ Intramolecular forces
 Control shape, function, and folding
 Weak in comparison to covalent bonds
◊ Hydrophobic interactions
► The tendency of greasy molecules to interact with non-aqueous substances
 Alanine
 Valine
 Phenylalanine
 Proline
 Isoleucine
► "Like dissolves like"
 Form almost a zipper-like connection
◊ Van der Waal interactions
◊ Hydrogen bonds
◊ Electrostatic interactions
► Ionic interactions
 Salt bridge
– Strongest long distance interactions in chemistry
 Quaternary structure
◊ The arrangement of the shapes into a larger protein
• Volatility
□ Conjugate bases
 Volatile because they aren't protonated
• Kb
A- + H2O --> OH- + HA

□ A- + H2O --> OH- + HA
 Kb is the constant when the weak base is the dominant species in the solution
◊ When the dominant species is the conjugate base to a weak acid

Lecture 5
Tuesday, April 06, 2010
9:56 AM
Lecture Topic:
• Acid base strength
○ Molecular structure
 Binary acids
□ Polarity
 More polar bonds = stronger acid
◊ High electronegativity difference = stronger acid
 Lower bond strength = stronger acid
 Oxoacids
□ Acidic oxides
 As the number of oxygen atoms attached to the central atom increases, the O-H bond
strength decreases
◊ Acid strength increases
 Nitrogen bases
• Acid base properties of salts
○ Cation
 Neutral
□ Anion
 Conjugate acid of weak base
◊ Basic
 Neutral
◊ Neutral
 Conjugate acid of weak base
□ Anion
 Conjugate acid of weak base
◊ acidic
 Neutral
◊ Acidic
• Lewis Acids and Bases
○ Lewis acid (A)
 Electron pair acceptor
○ Lewis base (B:)
 Electron pair donor
○ Adduct (B:A)
 Covalently bonded final product
○ Oxides
Acidic oxides

 Acidic oxides
□ When O-X bond is covalent
 Main group oxide (CO2, NO2, SO3, P4O10, etc.)
□ Forms acids in solution
□ Hydrolysis reactions
 No change in redox state
 Basic oxides
□ O-X bond is ionic
 Metals (MgO, Na2O)
□ Forms bases in solution
 React to form a salt
□ NO CHANGES IN REDOX STATE
 Only hydration/dehydration
○ Reactions
 Predicting reactions is easier if the reaction is not written in net ionic form
• Buffers
○ Contain relatively large amounts of weak acid and weak bases
 Added H+ reacts with the base
 OH- reacts with the acid
 pH is determined by the ratio of the concentration of the weak acid and base
○ Use limiting reactant issues
○ Resists changes in its pH

Lecture 6
Wednesday, April 07, 2010
10:00 AM

Ch 17: 15, 21, 28, 30, 45, 46, 49, 53, 57,
70, 77, 90, 95
Ch 18: 1, 4, 5, 6, 11, 15, 29
Read rest of 17 and 18.1-18.4
Lecture Topic:
• Buffers
○ Mixtures of weak acids or bases containing a common ion
 pH won't change upon dilution (good buffer)
□ Unless Kw can produce enough H+ or OH- to change [HA]0 or [A-]0
 Does not happen in a good buffer
○ Properties
 pH of the buffer is in the vicinity of the pKa of the weak acid
□ Within one log value
 Can use either Ka or Kb
□ pKa < 7
 Use Ka
□ pKa > 7
 Use Kb
 Henderson-Hasselbach equation
□ HA + H2O --> A- + H3O+
□ pH = pKa + log ([A-]/[HA])
 At equilibrium
 Used to calculate when [A-]/[HA]
 Volume of final solution not needed
○ Calculations
 Find initial conditions
 After addition of a strong acid or base, deal with limiting reactants first
□ Assume the strong acid or base reacts fully
 Then do equilibrium
 Write chemical reactions
 Equilibrium
□ Use ICE table

17.5-17.6
10:39 AM
• Acid-base equilibrium calculations

○ Species present and concentration
○ Identify the possible reactions between them
○ Find the stoichiometric and equilibrium constants

18.1-18.4
11:34 AM
• Solubility product constant

○ Ksp
 The constant for the equilibrium established between a solid solute and its ions
□ Saturated solution
 Relationship with solubility
○ Common-ion effect
 The solubility of a slightly soluble ionic compound is lowered by the presence of a second
solute that produces a common ion
○ Limitations
 Uncommon ion effect
□ Solubility increases
□ Salt effect
 The values of Ksp will depend on the ionic atmosphere and not on molarities
 Incomplete dissociation of solute into ions
□ Formation of ion pairs
 Happens when the solute is not 100% ionic
 True solubility is greater than Ksp

Lecture 7
9:58 AM
Lecture Topic:
• Titration curves
○ The neutralization point is where the pH radically changes
 The pH is 7 at this point
• Buffer capacity
○ Half-equivalence point
 Point half-way to the equivalence point
□ Important for titration of a weak acid + strong base
□ [HA] = [A-]
 For a weak acid
◊ [H+] = Ka
◊ pH = pKa
 For a weak base
◊ [OH-] = Kb
◊ pOH = pKb
□ Flattest part of the titration curve
 Equivalence point
□ Enough titrant has been added to exactly react (to completion) with the acid or base
○ Buffer regions in titration curves
 Optimal buffer capacity
□ It can accept acid or base
□ Conditions
 Typically one pH unit plus or minus the pKa or pKb
◊ .1 < [A-]/[HA] < 10
◊ pH = pKa + log([conjugate base]/[acid])
 Concentration of buffer is at least 100 times Ka
◊ Ensures that x is small
○ Indicators
 Marks the end point of a titration by changing color
□ The end point is just the point where it changes color
□ The end point is not necessarily the equivalence point
 Occurs when the color change happens before or after the equivalence point
◊ A buffer can change color within one pH unit of its pKa

◊ A buffer can change color within one pH unit of its pKa

Lecture 8
8:58 AM
Lecture Topic:
• Polyprotic acid and base equilibrium
○ Titrations
 Two equivalence points and regions for buffers
 Same regions as a weak acid/strong base titration
○ Ka
 Gets weaker as equations progress
□ As H+ ions are lost, the Ka decreases
□ The solution gets more basic because they are conjugate bases
○ Calculations
 Find major species
□ If H2A, use Ka1
□ If HA-, use Ka2
 Where HA- is predominant, compare Kb1 and Ka2 and use the larger one
 Final will be close to the average of the 2 Ka values
○ Total concentration = sum of concentrations of all species that might form
○ Sum of cation concentration = sum of concentration anions
• Amino acid titrations
○ Titrations
1. First step forms a cation(NH3+ --- COOH)
2. Second step forms the zwitterion (the NH3+ --- COO-)
1) Isoelectric point
a) pI = the pH at this point
b) The point at which the zwitterion is predominant
3. Third step forms an anion (NH2 --- COO-)
○ Sidechains
 Acidic
□ Glutamic acid
□ Aspartic Acid
 Basic
□ Histidine
□ Lysine
• Solubility
Solubility rules

○ Solubility rules
○ Ksp
 Evaluate molar solubility

Lecture 9
10:02 AM

Ch 27, 29, 39, 56
Ch 17: 72, 78, 90
Ch 18: 16, 26, 33, 38, 47, 50, 52, 53, 57,
73, 75, 76, 102
Lecture Topic:
• Solubility vs. Solubility product
○ Solubility
 Always a concentration
□ Not necessarily M
 Molar solubility
□ Concentration of 1 mole of the ions
□ Can change depending on the common-ion effect
○ Solubility product
 Ksp
□ Way of expressing solubility in terms of a constant
□ Follows all solubility rules
□ Higher value --> more soluble
□ Ksp based on number of ions
 2 ions
◊ Ksp = s^2
 3 ions
◊ 4s^3
 4 ions
◊ 27s^4
□ Predicting precipitation
 Use equilibrium quotient (Q)
◊ If K > Q
► Equilibrium is to the left
► Reaction will go to the right
◊ If K < Q
► Equilibrium is to the right
► Reaction will go to the left
◊ K= Q
► Reaction is at equilibrium
 For Ksp
◊ Q < Ksp
► Unsaturated solution
 No precipitate
◊ Q = Ksp

► Solution at equilibrium
► Saturated solution
◊ Q > Ksp
► Supersaturated solution
► Precipitate will occur
○ Complex ions
 A charged species consists of a metal ion surrounded by ligands (Lewis bases)
 Coordination number
□ Number of ligands attached to a metal ion

18.5-18.8
1:13 PM
• Criteria for precipitation

○ Q vs. Ksp
 Q > Ksp
□ Precipitation should occur
□ Solution is supersaturated
 Q < Ksp
□ Precipitation will not occur
□ Solution is not saturated
 Q = Ksp
□ Solution is exactly saturated
 If the remaining solute in the solution is less than 0.1% of the original solute present,
precipitation is considered to be complete
○ Fractional precipitation
 A technique in which two or more ions in solution are separated
□ Each ion is capable of being precipitated by the same reactant
□ One ion is precipitated while the others remain in solution
 There has to be a significant difference in the Ksp values of the ions
• Solubility and pH

Lecture 10
10:02 AM
Lecture Topic:
• Solubility
• Complex ion equilibrium
○ Complex ion
 A polyatomic ion composed of a central metal ion to which other groups are bonded
□ Bonded groups
 Ligands
 All are Lewis adducts
 Coordination
□ Coordination compound
 Substance that contains a complex ion
□ Coordination number
 Number of ligands attached to a metal ion
◊ 2, 4, or 6

Lecture 11
10:05 AM
Lecture Topic:
• Complex ions equilibrium
○ Kf
 Equilibrium constant of formation
○ Steps
 Chemical equation and stoichiometry
□ Find the final amount
 Equilibrium
□ Remember to use coefficients as exponents
 Find x by using Kf
□ Kf = Ksp * K1 * K2
 The equilibrium constants are multiplied when the equations are added

Lecture 12
2:57 PM

Ch 20.1-20.4
1, 5, 7, 10, 11, 18, 21, 22, 25, 34, 38, 44
Ch 20.5-20.8
51, 53, 55, 58, 59, 65, 73, 79, 85, 95, 99,
107
Lecture Topic:
• Complex ion equilibrium
• Buffering of blood pH
○ Aerobic life forms obtain energy for air oxidation of fuels to carbon dioxide
○ Blood pH
 Controlled at pH 7.4
□ Bone (slow)
□ Kidneys
□ Red blood cells
□ Lungs (fast)
□ Small molecules
□ Carbonate buffer
 Most important buffer in blood
□ Lactic acid
 Secreted by muscles during exercise
◊ CH3CHOHCOOH

20.6-20.8
Thursday, April 29, 2010
3:02 PM
• Electrolytic cells
○ Use electricity to produce a non-spontaneous reaction
 Electrolysis
○ Voltaic cell vs. electrolytic cell
 Voltaic
□ Oxidation
 A --> A+ + e-
□ Reduction
 B+ + e- --> B
□ Overall
 A + B+ --> A+ + B
 ΔG < 0
◊ Spontaneous redox
◊ Reaction releases energy
► System (cell) does work on the surroundings
 Electrolytic
□ Oxidation
 B --> B+ +e-
□ Reduction
 A+ + e- ---> A
□ Overall
 A+ + B --> B+ + A
 ΔG > 0
◊ Nonspontaneous redox
◊ Reaction absorbs energy to drive it
► Surroundings do work on the system

20.1-20.5
2:04 PM
• Electrode potentials and measurements

○ Electrode potential
 Electrode
□ Electrochemical cell
 Made of two half cells
 Half-cell
◊ A strip of metal that is immersed in a solution containing the ions of the
same metal
◊ Interactions
► Reduction
 A metal ion from solution may collide with the electrode
 Gains electrons
 Converted to a neutral metal ion
– Reduction is gain
► Oxidization
 The metal atom loses electrons to the electrode
 Becomes a positive metal ion
– Oxidation is loss
◊ Cannot use a wire because the charge is carried through solution by ions
► Must use a salt bridge
 A third solution in a U-tube that can carry ions
 Used to allow an ion flow in cases where the ionic form is not
stable
– Separates species that want to react spontaneously
 Voltaic/galvanic cells
◊ Produce electricity as a result of spontaneous chemical reactions
 Cell voltage
◊ EMF
► Cell potential
◊ Potential difference between the two half-cells
◊ The reading on the voltmeter
□ Anode vs. Cathode
 Oxidation takes place
◊ Anode
► Because the anode is negative, it will attract electrons away from
the ion
► On the left side of the diagram
► Electrons are on the right side of the reaction equation
► Negative ions from the salt bridge end up here
 Reduction takes place
◊ Cathode
► Because the cathode is positive, electrons will be attracted from it
to the less positive ion
► On the right side of the diagram
► Electrons are on the left side of the reaction equation
► Positive ions from the salt bridge end up here
 Electron flow is from the anode to the cathode

 Electrode potentials
□ Refers to only 1 M substance
 Don't multiply E by constants to accommodate constants]
□ Standard hydrogen electrode
 Equilibrium established on the surface of a inert metal between H3O+ ions from
solution
□ Standard electrode potential
 The tendency for a REDUCTION process to occur a an electrode
 Standard cell potential
◊ The voltage of a cell formed from two standard electrodes
► E(cell) = E(cathode/right/reduction) + E(anode/left/oxidation)
 Change signs for reactions that go backward
□ If ΔG increases, the E increases
□ Reactions and E
 If E(cell) > E(substance)
◊ E will react/displace that substance
 If E(cell) < E(substance)
◊ E will not react or displace the substance
• Relating E, G, and K
○ Faraday constant
 96, 485 C/mol electrons
○ ΔG = -n(electrons)FE(cell)
 E(cell) > 0
□ Reaction is spontaneous in the forward direction
 E(cell) < 0
□ Reaction is spontaneous in the reverse direction
 E(cell) = 0
□ Reaction is at equilibrium
 If reaction is reversed, E(cell) changes sign
○ E(cell) = (RT/nF) ln K
 Set the ΔG equations (ΔG = -RT ln K and ΔG = -nFE(cell) equal to each other
 Use R = 8.3145
 T is in Kelvin
 N is the number of electrons in the reaction
• Relating E(cell) to concentrations

○ E = E(cell) - (RT/nF) ln Q =
 E = E(cell) - (.0592/n) log Q
○ Concentration cell
 Two half-cells with IDENTICAL electrodes but different ion concentrations
• Batteries
○ A device that stores chemical energy for later release as electricity
 Types
□ Primary cells
 The cell reaction is not reversible
◊ When the reactants have mostly been converted to products, no more
electricity is produced
► Battery is dead
 Types
◊ Dry cell (LeClanche)
► Oxidation at a zinc anode
 Zn(s) --> Zn(2+) + 2e-

 Zn(s) --> Zn(2+) + 2e-
► Reduction at a graphite cathode
 2 MnO2 + H2O + 2e- --> Mn2O3 + 2OH-
► Electrolyte is a paste of MnO2, ZnCl2, NH4Cl and carbon
► Voltage slowly drops
 Zinc metal slowly dissolves because the electrolytic medium is
acidic
► Alkaline cell
 Also a dry cell
 Replaces NH4Cl with NaOH or KOH
 Reduction forms Zn(OH)2
□ Secondary cells
 The cell reaction can be reversed by passing electricity through the battery
◊ Charging
 Types
◊ Lead-acid/storage battery
► Capable of repeated use because of reversible reactions
► Restored by supplying electric current to recharge cells in the
battery
□ Flow batteries/fuel cells
 Reactants, products, and electrolytes pass through the battery
◊ Converts chemical energy to electrical energy
 Air batteries
◊ Oxidizing agent is O2
► Oxidizes a fuel like H2 or CH4

Lecture 13
10:04 AM

Review ΔG (Ch. 19)
Lecture Topic:
• Electrochemistry
○ 2H+ + Zn --> Zn2+ + H2
○ Gibbs' Free Energy
 If ΔG < 0
□ Spontaneous
 ΔG > 0
□ Nonspontaneous
 ΔG = 0
□ Equilibrium
○ Cell potential
 Maximum amount of work obtainable from a chemical reaction
 E(cell) > 0
□ Spontaneous
 SHE (standard hydrogen electrode)
□ A half-cell of hydrogen (H2)
□ E(cell) = 0
 2H+ + e- --> H2
 Voltaic cell
□ Consists of two half-cells
□ Electrons flow from anode to cathode
□ Anode
 Always the site of oxidation
 The negative electrode
◊ Where the overall potential is positive
□ Cathode
 The site of reduction
 The positive electrode
◊ The overall potential is negative
□ Discharging
 Ion movement is required for conduction
◊ Circuit is broken if bridge runs out
◊ Anode increases

◊ Anode increases
◊ Cathode decreses
◊ Driving force starts to go to 0
► ΔG = 0
 Equilibrium

Lecture 14
Tuesday, May 04, 2010
10:01 AM
Lecture Topic:
• Thermodynamics, equilibrium, and cell potential
○ Reduction potential
 E = Work/charge
□ E = -W/q
 Charge depends on how the work is done
◊ W + if work is done on the system by the surroundings
◊ W- if work is done on the surroundings by the system
 Q = nF
□ F = 94,486 C/mol
 ΔG° =nFE°
• Driving force in non-equilibrium conditions
○ ΔG° vs ΔG
 K vs. Q
 Proportional to E°
○ ΔG° = -RT ln K
 ΔG = -nFE°
 Therefore, E° = (RT/nF) ln K
○ Nernst
 ΔG = ΔG° + RT ln Q
□ RT ln Q is the adjustment factor for nom-standard conditions
□ When Q = K, ΔG = 0
 E = E° - (RT/nf) ln Q
□ E = E° - (.0592/n) log Q at STP (25 degrees celsius)
• Electrolytic cells
○ Energy is put into the system (so w is +)
• Batteries

Lecture 15
Wednesday, May 05, 2010
10:04 AM

Ch 14
1, 5, 6, 8, 11, 13, 15, 17, 21, 22, 23, 27,
29, 34, 43, 45
46, 49, 51, 57, 58, 61, 63, 64, 68, 70, 77,
86, 91
Lecture Topic:
• Batteries
○ Lead acid storage battery
 Pb + HSO4- --> PbSO4 + 2e- + H+
□ E = .356
□ Oxidation
 PbO2 + HSO4 + 3H+ + 2e- --> PbSO4 + H20
□ E = 1.685
□ Reduction
 E = 1.685 + .356 = 2.041
□ Discharging because E is +
 This battery is so awesome because it can quickly recharge itself
□ But it sucks because lead is so heavy
 The only concentrations that matter are the concentrations of the acid since the metals are solids
and not taken into account in the Q
□ Allows for constant voltage during discharge
○ Mercury batteries
 Zn(Hg) + 2OH- --> ZnO + H2O + 2e-
□ Anode
 Oxidation
 HgO + H2O + 2e- --> Hg + 2OH-
□ Cathode
 Reduction
○ Fuel cells
 2H2 + 4OH- --> 4H2O + 4e-
□ Anode
 Oxidation
 O2 + 2H2O + 4e- --> 4OH-
□ Cathode
 Reduction
• Corrosion
○ Iron
 Iron is oxidized
□ Anode
 Fe --> Fe2+ + 2e-
O2 is reduced

 O2 is reduced
□ Cathode
 O2 + 2H2O + 4e- --> 4OH-
• Concentration cells/neurochemistry
○ When the same components are in two half cells but in different concentrations
 Q = [diluted]/[concentration]
□ Spontaneous direction is towards dilution

14.1-14.6
Saturday, May 08, 2010
12:13 PM
• Chemical kinetics
○ Rate of a chemical reaction
 aA + bB --> gG + hH
□ Rate = -(1/a)[A]/t = (1/g)[G]/t
 Rate of formation
□ Always positive
 Rate of disappearance
□ Always negative
 Can be expressed as the slope of a tangent line
□ Instantaneous rate of reaction
 Initial rate of reaction
□ The tangent line to the concentration-time curve at t = 0
○ Rate law
 Rate = k*[A]^m*[B]^n
□ m and n are NOT the stoichiometric coefficients
 Order = m + n + …
◊ Zero order
► No effect on the initial reactant
► Rate = k[A]^0 = k
 Concentration-time graph is a straight line with a negative
slope
– Rate is the slope
► [A(time)] = -kt + [A(initial)]
► Line is A v. time
 K = -slope
 Half life = [A(initial)]/2k
◊ First order
► The initial rate doubles
► Line is ln [A] v. time
 K = -slope
► Rate = k[A]
 ln([A(time)/[A(initial)]) = -kt
– For gases [A] can be replaced with partial pressures
► Half-life
 The time required for half the reactant to be consumed
 T = (ln 2)/k = .693/k
 Constant for a first order reaction
◊ Second order
► The initial rate quadruples
► Line is 1/[A] v. time
 K = slope
► Half life = 1/k[A(initial)]
► Rate = k[A]^2
 1/[A(time)] = kt + 1/[A(initial)]
► Pseudo-first order reactions
 A second order reaction that behaves like a first order
reaction by holding one reactant concentration constant
 Can be treated like a first-order reaction
□ K is the rate constant
 Larger k means faster rate

14.7-14.11
2:35 PM
• Summary of reaction kinetics

1. When rate law is known, rate = k[A]^m[B]^n
2. To find rate when rate law is not known
i. Use the slope of a tangent line or -Δ[A]/Δt
3. To find the order of a reaction
i. Use the initial rates method if experimental rates are given
ii. Find the slope of the graph
iii. Test the constancy of the half life (only for first order)
iv. Substitute rate data into integrated rate laws to find a constant k
4. To find k
i. Obtain k from the slope of a straight line graph
ii. Substitute data into the appropriate rate law
iii. Obtain k from the half-life
5. To relate reactant concentration to time, find k and then use rate law
• Models for chemical kinetics

○ Collision theory
 Collision frequency
□ The number of molecular collisions per unit time
 Only a fraction of collisions among gas molecules lead to a reaction
◊ Every collision does not result in a reaction
 Activation energy
◊ The minimum energy that a molecule must bring to a collision for a
chemical reaction to occur
► Higher activation energy, smaller number of collisions, slower
reaction
○ Transition state theory
 A species is believed to exist in a transitory state that lies between the reactants and the
products
□ Transition state
□ The species is the activated complex
 Reaction profile
□ A graph in which energies are plotted on the vertical axis against the "progress of
reaction"
 The progress of reaction is the extent of the reaction
□ Enthalpy of a reaction is equal to the difference in activation energies of the forward
and reverse reactions
□ In an endothermic reaction, the activation energy must be greater than or equal to
the enthalpy
○ Effect of temperature
 ln k v 1/T is a straight line
□ ln(k2/k1) = Ea/R(1/t1-1/t2)
• Reaction mechanisms
○ A detailed description of a chemical reaction
 Each step is an elementary process
□ Describes any molecular event that significantly alters a molecule energy or geometry
or produces a new molecule

or produces a new molecule
□ Unimolecular v. bimolecular
 Either one molecule dissociates or two molecules collide
□ Exponents in rate laws are the SAME as the stoichiometric coefficients in the balanced
equation for the process
□ Reversible and some may reach equilibrium
□ Rate determining step is the slowest elementary step
○ Must be consistent with the stoichiometry of the overall reaction
○ Must account for the experimentally determined rate law
○ Reaction intermediate
 A substance that is created in one elementary process and reactant in another
• Catalysis
○ Catalyst
 Substance that lowers activation energy needed
 Does not undergo a permanent change so is not included in the overall reaction
○ Enzymes
 High molar mass proteins
 Substrates
□ A specific reacting substance that is catalyzed
○ Catalysis reactions
 Homogeneous
□ The reactants and products are present throughout the solution
 Heterogeneous
□ The catalyst is present in a different phase of matter
1. Adsorption
2. Diffusion
3. Reaction an at active site
4. Desorption

Lecture 16
Monday, May 10, 2010
8:37 AM

Quiz is over electrochemistry and
14.1-14.9
Lecture Topic:
• Concentration cells
○ Same components are in two half cells but are at different concentrations
 E(cell) = 0, ΔG = 0
 Can do work on surroundings if ΔG is negative and E is positive
□ Until Q = 0
 Galvanic until Q = 0
 Spontaneous direction is concentrated --> dilute
□ Q = [dilute]/[concentration]
 Goes until Q = K = 1
□ Dilute
 Oxidized
 Anode
□ Concentration
 Reduced
 Cathode
○ Neurochemistry
 Membrane of neuron is permeable to ions
□ Sodium/Calcium and Magnesium/Potassium
 If an imbalance of charge inside and outside the cell builds up, the potential that build up is balanced
out by the concentration potential
□ Nernst Potential
 E = E(cell) - (2.303RT/nF) log([K+(inside)]/[K+outside]) = 61.5*log([(outside)]/[(inside)])
◊ n (for an ion) is equal to charge
◊ At equilibrium, E = 0
 Potential
□ Depends on concentration of ions inside and outside the cell
 Permeability of the axon to these ions
• Thermodynamics vs. Kinetics
○ Thermodynamics
 Independent of pathway
 Does not examine the rate of the reaction
○ Kinetics
 Rate depends on the mechanism (the pathway)
□ The energetics of specific steps in the pathway
 Rate
□ Initial rate
Depends only on concentration of reactants

 Depends only on concentration of reactants
□ Rates
 Not constant
□ Rate law
 Concentration of reactants raised to powers which relate to their involvement in RATE
DETERMINING STEPS
 Exponents are derived from EXPERIMENTATION (not stoichiometry)

Lecture 17
8:40 AM
Lecture Topic:
• Rate laws
○ Relative rates
 Depends on stoichiometry
 A + 2B --> AB2
□ Rate = d[AB]/dt = -d[A]/dt = -(1/2)d[B]/dt
○ Determining rate laws
 Overall rate law
□ Depends completely on mechanism
□ Does not necessarily depend on stoichiometry
□ R = k[A]^x[B]^y[C]^z
 K is independent of concentration
 x, y, and z are established by experimentation
□ Order
 Sum of exponents
 Zero order
◊ Rate is constant
► Does not depend on concentration
► Typically found in gas phase reactions on surfaces
 Method of initial rates
□ Measure initial rate as tangent to curve in first instant
 Analytical fitting of data to integrated rate laws
□ Using regression
 Pseudo-first order reaction
□ The initial concentration of one reactant is MUCH higher than the others so it does not change
in the course of the reaction
○ Integrated rate laws
○ Half-lives
 The time at when concentration is at half of the initial concentration
 Zero order
□ Half life depends on concentration
 First order
□ Half life does not depend on concentration
□ Depends only on k
 Second order
□ Half life depends on concentration
○ Kinetic mechanism
 A series of elementary unimolecular/biomolecular steps in which intermediates form and decay

□ Add up to the reaction
 Rate law dictates the composition of the rate
 No overall product can be made until after the slow step

Lecture 18
10:02 AM

Ch. 24
1, 2, 5, 9, 12, 15, 16, 19, 20, 24, 29, 31,
32, 33, 36, 38, 39, 42, 44, 52, 55, 59, 76,
78
Lecture Topic:
• Collision theory
○ Activation energy
 Always positive
○ Effect of temperature
 As temperature increases
□ Distribution widens
 At higher temperature, more molecules have the amount of energy needed to undergo
reactions
 Catalyzed vs. uncatalyzed
□ As energy increases, number of collisions increases until activation energy is reached, and then
decreases
□ Catalyst
 Speeds up a reaction without being consumed
 Does not change thermodynamics
 Decreases activation barriers
 Types
◊ Homogeneous catalyst
► Same phase as reactants
◊ Heterogeneous catalyst
► Different phase
○ k = Ae^(-Ea/RT)
 A is the frequency factor
□ A = zp
 Z = collision frequency
 P = orientation factor
◊ Reactions only occur if the two molecules come together at the exact angle
 Ln (k2/k1) = (E/R)(1/T1 - 1/T2)
• Rate law
○ Activated complex
 The substance that exists at the top of a peak
• Psuedo-first order reaction
○ Complex rate laws can be simplified by holding all but one concentration constant
 For an element that is swamped, [A] = [A(initial)]
□ They won't change
• Mechanisms
○ Construction
Mechanism

 Mechanism
□ A set of elementary steps
 Uni/bi molecular reactions with relative rates
□ Show how the reaction occurs
□ Combine to give the overall stoichiometry
 Split things into radicals/ions and cancel them out
□ Focus on the slowest (rate-determining) step and the rate law
 Slow step must have all the reactants of the rate law on the left side
◊ They come together to form the activated complex
□ Check by deriving the rate law from the slow step
 Write the elementary rate expression for the slow step
 Substitute terms from fast step in

24.1-24.4
Friday, May 14, 2010
7:41 PM
• Coordination compounds
○ Crystals composed of two simpler compounds
○ Werner's theory
 Certain metal atoms, mostly those of transition metals, have two types of valence bonding
capacity
□ Primary valence
 Based on the number of electrons that the atom loses in forming the metal ion
□ Secondary valence
 Responsible for the bonding of other groups (ligands) to the central atom
◊ Complex
► Some substance that involves the coordination of ligands to a metal
center
► Coordination compounds
 Compounds of complexes
○ Coordination number
 The number of points around the metal center at which bonds to ligands can form
 6
□ Most common coordination number
 2
□ Limited to complexes of Cu (I), Ag (I), and Au (I)
○ Ligands
 Groups/side chains that bond to the central atom
 Have the ability to donate electron pairs to the central atom
□ Lewis bases
□ Central atoms are Lewis acids
□ Types
 Monodentate
◊ Uses one pair of electrons to form one point of attachment to the central
atom
 Polydentate
◊ Donate multiple electron pairs from DIFFERENT atoms in the ligand
◊ Donate to DIFFERENT points on the central atom
◊ Chelate
► The bonding of a polydentate ion produces a ring shaped structure
 The polydentate ion is a chelating agent
 Nomenclature
□ Anions
 -ide becomes -o
 -ite becomes -ito
 -ate becomes -ato
□ Neutral molecules
 Unmodified
□ Ligands that have a numerical prefix in their name
 Use parentheses and a different prefix
◊ 1 = mono
◊ 2 = bis
◊ 3 = tris
◊ 4 = tetrakis
□ Naming a complex
Ligands are named first in alphabetical order

 Ligands are named first in alphabetical order
 Central atom
◊ Oxidation state is noted by a roman numeral
 For the formula of a complex, the metal's name goes first
 Cations come first
○ Isomerism
 Isomers
□ Have the same formula but have different structures or properties
□ Types
 Structural
◊ Differ in basic structure or bond type
◊ Differ in which ligands are bonded to which atom
 Stereoisomers
◊ Have the same number and types of ligands and the same form of
attachment
◊ Differ in how the ligands space themselves around the central atom
 Isomerism
□ Ionization isomerism
 Coordination compounds that have the same central atom but differ in one
ligand
◊ The last ligand works to neutralize the charge of the central atom
□ Coordination isomerism
 A coordination compound that is composed of both complex cations and anions
◊ Ligands can be distributed differently between two complex ions
□ Linkage isomerism
 Ligands attach to the central metal ion of a complex ion through other atoms
◊ Depending on the atom, the properties change
□ Geometric
 Positions of the ligands produce different distinct isomers
□ Optical
 Compounds that can rotate the plane of polarized light
◊ Considered optically active
 Types
◊ Chiral vs. antichiral
► Chiral
 Nonsuperimposable
– Enantiomers
► Antichiral
 Can be superimposed
– Not isomers

24.5-24.11
11:57 AM
• Bonding in complex ions

○ Crystal field theory
 Bonding in a complex ion is considered to be an electrostatic attraction between the central
metal ion and electrons in the ligands
 Repulsion occurs between the ligand electrons and the d orbitals of the electrons
□ D orbitals
 The repulsions raise the orbitals' energy (d(z^2) and d(x^2-y^2))
◊ Crystal field splitting
► The energy of the other 3 d orbitals is lowered in order to
accommodate the increase
► Difference in energy is expressed by Δ
◊ Tetrahedral
► Dxy, dyz, and dxy are higher than dz^2 and dx^2-y^2
◊ Octahedral
► Dz^2 and dx^2-y^2 are higher than dxy, dyz, and dxz
□ Pairing energy
 The energy required to force an electron into an unpaired electron's orbital
 The addition of an electron to the d orbital gives the complex extra energy
 Spin
◊ Low
► Δ>P
 Greater stability is obtained by putting the fourth electron
with one in a lower level
 Corresponds to the minimum number of unpaired electrons
 Ligands with large crystal field splitting
– Strong field
◊ High
► Δ<P
 Greater stability is obtained by leaving the electron unpaired
 Maximum number of unpaired electrons
 Ligands with small crystal field splitting
– Weak fields
 Spectrochemical series
◊ The arrangement of ligands to produce splitting of the d energy levels
○ Magnetic properties
 Paramagnetism vs. diamagnetism
□ High spin
 Highly paramagnetic
□ Low spin
 Weakly paramagnetic or diamagnetic
○ Complex ion equilibrium
 Hydrates
□ A compound with water molecules bonded to it
 To form a new complex, water must be displaced
 As hydrates are removed, stability increases
□ K increases
□ Chelation effect
Chelates are more stable than complexes with monodentate ligands

Chelation effect
 Chelates are more stable than complexes with monodentate ligands
 Acid base reactions
□ A higher charge on a central atom is a stronger acid
 Compounds have higher Ka
○ Kinetic considerations
 Labile
□ Coordination compounds that can rapidly change their ligands
 Nonlabile/inert
□ Slowly change ligands

Lecture 19
9:57 AM

Quiz: 23.1, 24.1-24.6, enzyme/catalytics
Lecture Topic:
• Enzyme catalysis
○ Mechanisms
 Propose a mechanism by starting with the activated complex
□ Activated complex is always present in the slow step
 Slow step is dictated by activated complex
 Activated complex has a formula that matches the rate law
◊ Use coefficients to find number of atoms needed
 Activated complex exists only for an instant and can't be detected
○ Rate vs. concentration
 Michaelis-Menten equation
□ V0 = (k(slow step)*E[total][S])/(K m+ [S])
 Km = [E][S]/[E-S]
◊ Higher Km, weaker binding
◊ If S is small, [S] <<<<< Km
► V0 = (k(slow)*[Etotal][S])/[Km)
◊ If S >>>>> Km
► V0 = k(slow)[Etotal]
□ Rate becomes independent of substrate
 Rate saturation
◊ There is a rapid pre-equilibrium intermediate that can be saturated
□ R = k*K[E(total]-[E-S])[S]
 If [S] is small, Etotal >> E-S
◊ r = k(slow step)*K[Etotal][S]
► K = 1/Km
 Rate = v
 Initial rate = v0
 Mechanism
1. Fast equilibrium
a) E + S <-->E-S
2. Slow step
a) E-S --> E + P
 Substrate (S) concentration is always greater than the enzyme concentration (E)
• Coordination chemistry
Transition metal

○ Transition metal
 Size increases when going down a period
 Size decreases when going to the right of a row
 Adding positive charge to a nucleus increases charge
□ Electron cloud is pulled in
 Radius goes down
○ Lanthanides/actinides
 Have f orbitals
 Lanthanide contraction
□ Second and third row transition metals are the same size

23.1
10:47 AM
• Transition elements
○ General properties
 High melting points
 Good conductivity
 Moderate to extreme hardness
 Atomic radius
□ Lanthanide contraction
 The atomic radius does not differ much between the second and third rows of
the transition metal series because of the addition of the lanthanides
 Ionization energies
□ Stay relatively constant across the transition metals
○ Catalytic activity
 Some metals can adsorb gaseous species making them good heterogeneous catalysts
□ Platinum
○ Ferromagnetism
 The ability to be made into a permanent magnet

Lecture 20
8:40 AM
Lecture Topic:
• Coordination chemistry
○ Oxidation States and electron configurations
 Ionization energy increases as more electrons are removed
 Oxidation numbers
□ The number of oxidation states is equal to the group number (up to manganese)
□ Transition metals (other than zinc) all have +2 and +3 oxidation states
 Electron numbers and color
□ Higher oxidation state means higher wavelength (toward red side)
 Electron configuration for transition metals
□ Valence electrons consist of unpaired electrons and s orbital electrons
□ For +2 ions in transition series
 4s orbital will be at a higher energy than the 3d orbital
◊ But only for +2 ions
○ Coordinate covalent bonds
 Complex ions
□ Metal ions bound to neutral molecules and negative ions through coordinate covalent bonds
 Coordinate covalent bond
◊ The metal is the Lewis acid
◊ Both electrons are donated by a ligand (Lewis base)
► Ligands must have an unshared pair of electrons
 Ligands
□ Types
 Bidentate
◊ Two donor atoms in one molecule that each donate a pair of electrons
 Monodentate
◊ One atom that donates a pair of electrons
□ Specific ligands
 H20
 NH3
 CN-
 NO2
 SCN-
 OH-
 Halides
 Ethylenediamine
◊ Chelating agent

◊ Neutral (charge is 0)
◊ Attaches by two nitrogens
 Oxalate
◊ Chelating agent
◊ Dianion (charge is -2)
◊ Attaches by two oxygens
 Diethelyenetriamine
◊ Tridentate
 Ethylenediaminetetraacetate
◊ Chelating agent
◊ EDTA
◊ 6 coordinating atoms
◊ A single ethylenediamine with 4 acetates bound to it
◊ -4 charge and binds to a +2 metal ion
○ Coordination number
 Bonding
□ Hybridize the empty orbitals
□ Number of bonding ligands equals number of hybrid orbitals
□ Cr
 4s13d5
 Numbers and geometry
□ 2
 Linear
◊ sp
□ 4
 Tetrahedral
◊ Sp3
◊ No geometric isomers
► Nothing can distinguish one side from the other
 All angles are 109 degrees
◊ Can have optical isomers if all four ligands are different
 Square planar
◊ Dsp2
◊ Platinum II is always square planar
◊ Have geometric cis-trans isomers
► Differ in the angles
□ 6
 Octahedral
◊ Sp3d2
○ Stereochemistry
 Isomerism
□ Types
 Structural
◊ Coordination
► Atoms are bonded to different atoms
 Same atoms, but in one case, can be bonded to the central atom or to
a ligand
◊ Linkage
 Stereoisomers
◊ Geometric
Cis-trans

► Cis-trans
◊ Optical

Lecture 21
3:01 PM

Quiz up to 24.4
Lecture Topic:
• Isomers
○ Isomers are only affected by compounds that are not bonded to the central atom IF that outside ligand
directly affects one of the central ligands
○ Stereoisomers
 Geometric
□ Not tetrahedral molecules
□ Cis vs. trans (octahedral)
 Cis
◊ The group of 2 is located on the top and on one of the corners (top right)
 Trans
◊ The group of 2 is located on the top and bottom
□ Cis vs. trans (square planar)
 Cis
◊ Two of the same ligand are on each side of the square planar molecule
 Trans
◊ Two of the same ligand are on the diagonals of the square planar molecule
□ Mer vs. fac (octahedral)
 Requires 3 of the same ligands bound to the central atom
 Mer
◊ One of the three is on a corner (top right)
◊ Two of the three are on top and bottom
 Fac
◊ All linkages are cis links
◊ One of the three is on the top
◊ Two of the three are on corners (top right and bottom right)
 Optical isomers
○ Linkage isomers
 Differ in the bond order of linkage
□ NO2 vs. ONO

Lecture 22
2:55 PM

Quiz on Ch 24, Ch 18 (complex ion
formation), Ch. 14, Ch 27 (enzymes and
Important Proteins mechanisms)
Carbonic Anhydrase Review enzyme/mechanisms
Superoxide Dismutase (carboxypeptidase)
Hemoglobin Review complex ion formation
Lecture Topic:
• Crystal field theory
○ The atomic orbitals of the metal center (the d-orbitals) cause a repulsive interaction between ligands that
are attached
 Results in destabilized d-orbital energies
 Approach
□ Look at d-orbitals as negative charges
 Atomic orbitals which point at ligands (dz^2 and dx^2-y^2) encounter more direct
repulsion forces and are more destabilized
◊ Point directly on axis
◊ Eg orbitals
 dxz, dxy, and dyz are not as destabilized
◊ T2g orbitals
 Strong field vs. weak field
□ Strong field
 Large electron pairing energy
◊ The energy it takes to put 2 electrons in an orbital
 Fill low energy levels first
◊ Lower levels are paired first
◊ Diamagnetic
 Form low spin
□ Weak field
 Small electron pairing energy
 Fill all orbitals before pairing
 High spin complex
◊ Paramagnetic
□ Spectrum
 Weak field to strong field (high spin to low spin)
◊ Cl-
◊ F-
◊ H20
◊ NH3
◊ En
◊ NO2-
◊ CN-
Color of transition metal complexes

○ Color of transition metal complexes
 When energy is high, wavelength is low
□ Absorbed energy is opposite to the transmitted light
 E = hv = hc/λ
□ Proportional to ligand field strength
 Paramagnetism
□ Low field strength
□ Light absorbed has a longer wavelength
• Chelate effect
○ Formation constants

Lecture 23
2:55 PM
Lecture Topic:
• Chelate effect
○ Kf
 Higher Kf means that it will displace a lower Kf in bonds
 Driving force and H, S
□ More negative H makes it a stronger driving force
□ More positive S makes it delay the driving force
○ Chelate effect relies on entropy terms
• Biological coordination chemistry
○ Hemoglobin
 Responsible for transport of O2
 Consists of 4 heme polypeptides
 Delocalized orbitals
 Contains iron
□ Binds 4 O2 molecules and forms a bright red diamagnetic complex
□ Looks like a cis isomer
 Fe in the middle and bonded to nitrogen
◊ Fe is both iron II and iron III
 Works better at basic pH
 Allosteric
□ Compounds that bind to hemoglobin at a site far from the O2
○ Metal ion catalysis
 Carbonic anhydrase
□ Contains Zn
 Accelerates CO2 hydration
□ Kcat = 10^-6 1/s

Lecture 24
8:11 AM

Overview of final
Bicarbonate chemistry
Physiological acid-base reaction
Polypeptides and esters
Kinetic characteristics of enzymes
Coordination chemistry of biological
molecules
Metalloenzymes (hemoglobin, carbonic
anhydrase, copper zinc superoxide
dismutase)
Lecture Topic:
• Metalloenzymes
○ Catalytic mechanisms
 Cu, Zn superoxide dismutase
□ Dismutase reaction
 Disproportionation reaction (uncatalyzed)
◊ No electron transfer
◊ Favorable thermodynamics
◊ Fast kinetics
 Converts superoxide (O2-) to hydrogen peroxide which turns into water
 Reactions
◊ Cu2+ + O2 - --> Cu+ + O2
► Cu 2+ oxidizes O2- to O2
◊ Cu+ + O2- + 2H+ --> Cu2+ + H2O2
► Cu 2+ reduces O2 to H2O2
• General acid base catalysis
○ Titration curves of amino acids
 Glutamic acid
□ pKa = 4.3
□ Carboxylic acid side chain
 pKa is between 2-4
 Lysine
□ pKa = 10.5
□ Amine side chain
 pKa is between 7-9
○ Fundamentals of amino acid structure
○ pI for an amino acid and a protein
 pI is the pH at which the protein has no net charge
 If pH < pKa of amino acid
□ Charge is + or neutral
□ Loses an electron
 If pH > pKa of amino acid
Charge is - or neutral

□ Charge is - or neutral
□ Gains an electron

Chemistry 103

Transféré par

Informations du document

Description originale:

Copyright

Formats disponibles

Partager ce document

Partager ou intégrer le document

Options de partage

Avez-vous trouvé ce document utile ?

Ce contenu est-il inapproprié ?

Droits d'auteur :

Formats disponibles

Chemistry 103

Transféré par

Droits d'auteur :

Formats disponibles

27.1-27.2, 27.

• Chemical structure of living matter

Chemistry 103 Page 1

Chemistry 103 Page 2

Chemistry 103 Page 3

• Strong/Weak Acids and Bases

Chemistry 103 Page 4

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 5

Chemistry 103 Page 6

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 7

Chemistry 103 Page 8

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 9

Chemistry 103 Page 10

• Ions as acids or bases

• Molecular structure and acid-base behavior

Chemistry 103 Page 11

• Lewis acids and bases

Chemistry 103 Page 12

Chemistry 103 Page 13

• Neutralization reactions and titration curves

1. Initial pH is high (less acidic) than it is in the titration of a strong acid

Chemistry 103 Page 14

Chemistry 103 Page 15

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 16

Chemistry 103 Page 17

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 18

Chemistry 103 Page 19

Formulas & Theorems Covered Today: Homework:

Read rest of 17 and 18.1-18.4

Chemistry 103 Page 20

• Acid-base equilibrium calculations

Chemistry 103 Page 21

• Solubility product constant

Chemistry 103 Page 22

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 23

Chemistry 103 Page 24

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 25

Chemistry 103 Page 26

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 27

Chemistry 103 Page 28

• Criteria for precipitation

Chemistry 103 Page 29

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 30

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 31

Formulas & Theorems Covered Today: Homework:

Chemistry 103 Page 32

Chemistry 103 Page 33

• Electrode potentials and measurements

Chemistry 103 Page 34

• Relating E(cell) to concentrations

Chemistry 103 Page 35

Chemistry 103 Page 36

Formulas & Theorems Covered Today: Homework: