Académique Documents
Professionnel Documents
Culture Documents
Concentration-Time Graph
Rate at any point can be found by drawing a tangent at that point on the graph
and finding the gradient.
Orders of Reaction
The order of reaction = how the reactants concentration affects the rate
INCREASE REACTANT RATE STAYS THE SAME ORDER OF 0
INCREASE REACTANT RATE INCREASES BY 1 FACTOR ORDER OF 1
INCREASE REACTANT RATE INCREASES BY 2 FACTORS ORDER OF 2
You can only find the order of a reaction *experimentally* there is NO
theoretical order system.
Column
2
6
5
4
3
2
1
0
time (s)
Column
2
Column
2
6
5
4
3
2
1
0
[X]
Column
2
5
4
3
2
1
0
[X]
6
5
4
3
2
1
0
time (s)
Column
2
10
5
Column2
0
[X]
ZERO ORDER
FIRST ORDER
SECOND ORDER
n = order of B
n+m = overall order
k = rate constant (always the same for a reaction at specific temp and pressure,
increase temp = increase k = bigger value of k = faster reaction)
EXAMPLE
Propanone + Iodine > Iodopropanone + H + + Iacid)
(reaction occurs in
Info: First order with respect to propanone and H + and zero order with respect to
iodine
Rate equation = k[propanone]1[H+]1[iodine]0
Simplify to;
Rate equation = k[propanone][H+]
0 is 1)
Change compared
to experiment 1
--[propanone]
doubled
[propanone]
trebled
Rate of reaction
Change
0.033
0.062
--Rate doubled
0.092
Rate trebled
4
5
6
7
[iodine] doubled
[iodine] trebled
[H+] doubled
[H+] doubled
0.034
0.032
0.058
0.094
No change
No change
Rate doubled
Rate trebled
*Reaction rates wont be exactly double or treble due to experimental errors etc.
4) Now we can work out the rate equation:
fast reaction
Therefore, Cl and O3 must be in the rate equation as they are the reactants from
the slowest step.
RATE = k[Cl][O3]
Predicting Mechanisms:
Once you know what the rate determining reactants are, you can think about
what reaction mechanism it follows.
EXAMPLE:
If the rate equation is: rate = k[X][Y]
And the two different mechanisms are:
1) X + Y > Z
OR
2) X > Y + Z
From the rate equation, we know that X and Y MUST be in the rate determining
step, therefore, its mechanism 1 which is the right one.
You can see by the rate equation if there are 1 or 2 molecules in the rate
determining step, which in turn, tells you if the mechanism is SN1 or SN2.
EXAMPLE:
Rate = k[X][Y] = 2 molecules in rate determining step = SN2 =
primary/secondary halogenoalkane
OR
Rate = k[X] = 1 molecule in rate determining step = SN1 = tertiary/secondary
halogenoalkane
Activation Energy
We can calculate the activation energy using the Arrhenius equation:
Where;
the relationship)
k = rate constant
T = temperature (K)
A = another constant
Some relationships to note:
1) As EA increases, k will get smaller. Therefore large activation energy,
means a slow rate this makes sense!
2) As T increases, k increases. Therefore at high temperatures, rate will be
quicker this makes sense too!
If we ln both sides of Arrhenius equation,
we get;
ln k = EA/RT + ln A
(dont forget, ln A is just a constant, a
number)
and
for
Catalysts
Catalyst = increases rate of a reaction by providing an alternative reaction
pathway with a LOWER activation energy (E A). A catalyst will be chemically
unchanged at the end of a reaction.
Adv: Small amount needed to catalyse a lot of reactions, also they are remade,
thus reusable.
Disadv: High specificity to the reactions they catalyse.
There are two types of catalysts:
HOMOGENOUS CATALYSTS
These are catalysts in the same state
as the reactants.
E.G. when enzymes catalyse reactions
in your body, all reactants are aqueous,
this is a homogenous catalysis.
HETEROGENOUS CATALYSTS
These are catalysts in different physical
states to the reactants.
They are easily separated from
products GOOD
Can be poisoned (i.e. a substance
clings to a catalyst stronger than the
reactant would, preventing reaction
speeding up) example: sulphur in the
Haber process is a poison BAD
Solid catalysts provide a large surface
area for the reaction to occur e.g.
mesh/powder
E.G. vanadium pentoxide in the contact
process to make sulphuric acid
4.2 Entropy
Entropy = a measure of how much disorder there is in a substance, how many
different ways particles can be arranged.
Systems are MORE energetically stable when disorder/entropy is HIGH.
EXAMPLE: A gas will want to escape its bottle because the room its in is much
bigger and the particles can be arranged in lots of different ways.
SOLID
LIQUID
GAS
No randomness,
Some randomness, some Most randomness,
therefore lowest entropy. entropy.
highest entropy.
e.g. S (H2O(s)) = 7.4 JKe.g. S (H2O(l)) = 70 JKe.g. S (H2O(g)) = 189 JK1
1
1
mol-1
mol-1
mol-1
(see below)
(see below)
(see below)
*Note that zero entropy will only occur in a perfectly ordered crystal
Affecting Factors:
1. More quanta (packets of energy) = More ways to arrange particles = More
entropy
2. More particles = More arrangements = More entropy.
E.G. X -> 2Y 2 moles of Y produced from 1 mole of X therefore entropy has
increased
3. Increase in temperature = Increase in energy = More entropy
E.G.
bit
H+(aq) >
1 mole
Na+(aq)
1 mole
1 mole
CO2(g)
1 mole
H2O(l)
1 mole
Solid
aqueous ions
aqueous ions
gas
liquid
Here, the products have high entropy states (e.g. gas) and there are more moles
(e.g. reactants to products = 2:3) And so, overall entropy has increased =
SPONTANEOUS (also depends on H see below)
LEARN THESE:
HCl(g)
>
NH4Cl(s)
H = -315kJmol-
Info:
1
1)
Ssys
= Sproducts - Sreactants
= - (-315000)/298
therefore x1000]
= + 1057 JK-1mol-1
3) Find total entropy
Stotal
= Ssys + Ssurr
= -284.5 + 1057
= + 772.5 JK-1mol-1
answer]
+ S
total
total
* You can predict ionic compound solubility using the same idea; if S total is
positive , if negative X
ENDOTHERMIC experiments that are spontaneous:
1) Ba(OH)2(s) and NH2Cl(s)
Ba(OH)2.8H2O(s)
2NH2Cl(s)
>
BaCl2(s) +
10H2O(l) +
2NH3(g)
H2O(l)> NH4+(aq) +
NO3-(aq)
Kinetic inertness when the Stotal of a reaction is positive, a reaction can happen
spontaneously, however the rate of reaction at RTP is so slow because the
activation energy needed for it to start is so high. E.G. diamond > graphite
The enthalpy change of hydration, Hhyd the enthalpy change when 1 mole of
aqueous ions is formed from gaseous ions. E.G. Na +(g) > Na+(aq)
The standard lattice enthalpy, Hlatt the enthalpy change when 1 mole of a
solid ionic compound is formed from gaseous ions under standard conditions
(298K and 1atm). E.G. Na+(g) + Cl-(g)> NaCl(s)
The enthalpy change of solution, Hsol the enthalpy change when 1 mole of
solute is dissolved in sufficient solvent, so no further enthalpy change occurs on
further dilution. E.G. NaCl(s) > NaCl(aq)
Factors affecting Hlatt AND Hhyd include;
1) Ionic charge;
= larger charge
= more exothermic lattice energy
= MORE NEGATIVE LATTICE ENTHALPY/ENTHALPY OF
HYDRATION
E.G. NaCl has Hlatt = -780kJmol-1 whereas MgCl2 has Hlatt = -2526kJmol-1
because magnesium has a charge of 2+ which is greater than sodiums
1+
2) Ionic radii;
H1 = H2 + H3
REMEMBER (for Hsol ): GASEOUS IONS DOWN, AQUEOUS IONS UP
Guns In
4.3 Equilibria
RECAP: (for exothermic reaction)
LE CHATELIER
oppose the
motion!
Increase
Temperature
Increase Pressure
Introduce Catalyst
2SO3(g)
2NH3(g)
(REVERSIBLE)
H2(g) + I2(g)
2HI(g)
Initial concentration:
H2 = 1.0moldm-3
Equilibrium concentration:
H2 = 0.228moldm-3 I2 = 0.228moldm-3
I2 = 1.0moldm-3
From this we can see that the ratio has remained the same, i.e. 1:1
Kp / Kc
What is Kp / Kc?
K p / Kc is the ratio of product concentration to reactant
concentration, and is commonly known as the
equilibrium
constant. For example, in the hydrogen-iodine reaction K c will be;
*Note: products are
below
E.G. 4X
2Y + 3Z
EXPERIMENT:
Fe2+(aq) + Ag+(aq)
Fe3+(aq) + Ag(s)
CALCULATION:
Reactant/Product
Initial concentration
(moldm-3)
Equilibrium
concentration
(from titre results)
Equilibrium constant
Fe2+(aq)
0.05
Ag+(aq)
0.05
Fe3+(aq)
0
Ag(s)
0
0.0439
0.0439
(1:1 ratio)
0.0061
(0.05
0.0439)
solid
Units
EXAMPLE:
When 3.0 moles of PCl5 is heated in a closed system, the equilibrium mixture has
1.75 moles of Cl. If total pressure of the mixture is 714kPa, what is the partial
pressure of PCl5?
Step 1) Find moles at equilibrium of all reactants and products;
We know 1.75 moles of Cl2, therefore we must also have 1.75 moles of PCl 3 and
so (3 - 1.75) will leave us with the moles at equilibrium for PCl 5 which is 1.25
moles. Adding these together we get 1.25+1.75+1.75 = 4.75 total moles at
equilibrium.
Step 2) Find the mole fraction;
Mole fraction of a gas in mixture =
1.25
4.75
5
19
= 1.66
5
19
= 187.9kPa
Stotal = R lnK
When the total entropy, Stotal, increases, the equilibrium constant, K, will also
increase.
If;
From the timeline we can see the change in definition of acids through history.
The main ones to know are:
Arrhenius definition when acids/bases dissolve in water then
completely/partially dissociate into charged particles (ions)
BrnstedLowry definition an acid is a proton donor and a base is a proton
acceptor; acids (proton donors) will never release a H + on its own, it is always
combined with H2O to form HYDROXONIUM IONS H3O+
*NOTE: Acid-base equilibria involves the transfer of protons, either donated or
accepted.
Strong
Acid
example
HCl(g) > H+(aq) + Cl-(aq)
NaOH(s) + H2O(l) > Na+(aq) +
OH-(aq)
reason
Strong acids and bases ionise
almost completely in water.
*HCl has a pH of 0 =
completely ionised
CH3COOH(aq)
CH3COO-(aq) +
H+(aq)
NH3(aq) + H2O(l)
NH4+(aq) +
OH-(aq)
Base
Weak
Acid
Base
WATER is special it can behave as a base and an acid. You can work out the
equilibrium constant in the same manner as we did before e.g.
However, the equilibrium is very far left and so the equilibrium constant for this
reaction is said to have a constant value;
pH = - log
CALCULATION: finding the pH of a strong acid
1) Calculate the pH of 0.05 moldm-3 of nitric acid.
pH = - log[H+]
pH = - log[0.05]
= 1.3
acid)
2) An acid has a pH of 2.45, what is the hydrogen ion concentration?
pH = - log[H+]
[H+] = 10-pH
= 3.55 x 10-3 moldm-3
*NOTE: H2SO4 dissociates to give 2[H+] and you will have to divide the final
answer by 2 to find your hydrogen ion concentration
CALCULATION: finding the pH of a weak acid
Weak acids do not fully dissociate so it isnt as straight forward as above.
Another constant called Ka is introduced. There are some assumptions to make
first:
a) Only a tiny amount of product dissociates so initial concentration of reactant =
equilibrium concentration of reactant
b) All H+ ions come from the acid i.e. concentration of product 1 = concentration
of product 2
1) Calculate the hydrogen ion concentration and the pH of a 0.02 moldm -3
solution of propanoic acid (CH3CH2COOH). The Ka of propanoic acid is 1.3 x 105
moldm-3.
Ka = [H+]2/[CH3CH2COOH]
[H+] = 5.09 x 10-4
pH = -log[5.09 x 10-4]
pH = 3.29
[H+] =
OH
Kw
1.0 x 1014
0.1
Therefore,
pH = -log [1.0 x 10-13]
= 13.0
(ph value is large expected for a strong alkali)
CALCULATION: finding the pKa
pKa = - log
1) Calculate the pH of 0.05moldm-3 of methanoic acid (HCOOH). Methanoic
acid has a pKa of 3.75.
3.75 = -log[Ka]
Ka = 1.78 x 10-4
pH = -log[2.98 x 10-3]
pH = 2.53
*end point: when the solution changes colour (also known as equivalence point
see below)
INDICATORS
Indicator
Colour in
acid
Methyl
orange
phenolphthal
ein
red
colourles
s
pH when
colour
change
3.1-4.4
Colour in
alkali
8.3-10
pink
yellow
acid
pH
scalealkali
pH Curves
Strong acid/Strong
alkali
Phenolphthalein
indicator
Weak acid/Strong
alkali
Strong acid/Weak
alkali
Methyl orange
indicator
Weak acid/Weak
alkali
Phenolphthalein
indicator
Equivalence point = where a tiny amount of alkali causes a sudden big change in
pH, where the acid is JUST neutralised. Equivalence point will vary depending on
acid/alkali used. For the last graph between a weak acid and weak alkali, a pH
meter is the best thing to use to find the equivalence point as the colour change
is gradual and unclear.
CALCULATION: finding the Ka of a weak acid using a pH curve
Buffers
-
ACIDIC BUFFERS
Weak acid + Salt
CH3COO-Na+(aq)> CH3COO-(aq) +
Na+(aq)
This fully dissociates; therefore
mostly ethanoate ions
-
CH3COOH(aq)
CH3COO (aq) + H
(aq)
This only slightly dissociates;
therefore mostly ethanoic acid
ADDING ACID: (small amount)
[H+] increases which combines with
the CH3COO- to form CH3COOH so
equilibrium shifts to left, no change in
pH.
ADDING ALKALI: (small amount)
[OH-] increases which combines with
the H+ to form H2O which removes the
H+ ions from solution, so more H+
dissociate from CH3COOH so
equilibrium shifts to right, no change
in pH.
ALKALINE BUFFERS
Weak base + Salt
NH4Cl(aq)> NH4+(aq) + Cl -(aq)
This fully dissociates; therefore mostly
ammonium ions
NH4+(aq)
H+(aq) + NH3(aq)
This only slightly dissociates; therefore
mostly ammonium
Buffer
Cells need
constant pH for
biochemical
reactions to take
place
Controlled by the
equilibrium
between
dihydrogen
phosphate and
hydrogen
phosphate
H2PO4HPO42-
Sodium citrate
H2CO3
H2O + CO2
Lungs - by breathing out
CO2, levels of H2CO3
decrease and so
equilibrium moves to the
right
Citric acid
citrate ions
Or
Phosphoric acid
phosphate ions
Or
Benzoic acid
benzoate ions
H+ +
H2CO3
H+ + HCO3-
CALCULATION:
A buffer solution of 0.4 moldm-3 of
1. Equation for Ka
2. Rearranging
3. Find pH
Optical
E/Z
rotation
*known as
is
restricted
fixed in position.
enantiomers
Z-ISOMER
E-
ISOMER
groups attached to it.
TRANS opposite sides
They are optically active (they rotate
CIS
same
determined
by
side
how
the heaviest
plane-polarised light) one will rotate
distributed around
molecules
are
Aldehydes and
Ketones
H+ + CN-
Info
2,4dinitropheylhydrazine
Ketone
Orange
Aldehyde
Orange
Tollens reagent
+ heat (water bath
not flame as
flammable!)
Colourless solution of
silver nitrate dissolved
in ammonia which gets
reduced and changes
colour;
No change
Silver mirror
(Ag(s))
Aldehyde
oxidised
No change
Brick red
Fehlings/Benedicts
Ag(NH3)2+(aq) + e-
> Ag(s) +2NH3 (aq)
Blue solution of
solutions
copper(II) ions
dissolved in NaOH(aq)
become Cu+ ions;
precipitate (Cu+
ions)
Aldehyde oxidised
Iodine in alkali +
heat
(tests for CH3 on
carbon attached to
oxygen)
*NOTE: Bradys: you can identify carbonyl compounds by the melting point of the
orange precipitate against known values
OXIDISING
Aldehyde > Carboxylic acid [heat with acidified potassium dichromate (VI)
ions (oxidising agent)]
colour change:
ORANGE to GREEN
Ketone > Carboxylic acid X [acidified dichromate (VI) ions are not a strong
enough oxidising agent]
REDUCING: [LiAlH4 in dry ether]
Aldehyde > Primary alcohol
Carboxylic
Acids
They hydrogen bond with themselves as they do have a polar O-H+ bond. For
this reason, carboxylic acids have very high boiling points.
They can hydrogen bond with water due to their polar C+=O- bond. Oxygen
uses its lone pair to form hydrogen bonds with H+ atoms on the water
molecules. Therefore, carboxylic acids are soluble, however as they get bigger
they become less soluble as the intermolecular forces get too strong.
Dimer:
effervescence
2) 2CH3COOH + Na2CO3 > 2CH3COONa + H2O + CO2
E.G. 12.5 ml of 0.1 moldm-3 of NaOH exactly neutralises 25ml of
orange juice. What is the concentration of citric acid in the juice?
3NaOH + C6H8O7 > Na3C6H5O7 + 3H2O
1) Find moles
mols = conc x vol = 0.0125 x 0.1 =
0.00125mols
2) Find ratio/moles 3mol NaOH neutralised 1mol citric acid; 3:1
0.00125 3 = 0.000417mol
3) Find concentration
conc = mols vol
0.025 0.000417 = 0.017 moldm-3
Reduction; 1) CH3COOH LiAlH4 (in dry ether)> 2CH3OH
2) CH3COOH + PCl5 > CH3COCl + POCl3 + HCl
ethanoic acid
ethyl chloride
Making an ester:
Carboxylic acid + alcohol (heat/reflux/acid catalyst)
ester
It is a reversible reaction so in order to get the ester you must distil off the liquid
at 80C, and then mix with sodium hydrogen carbonate solution to remove any
acid. Then separate the top layer (ester) using a funnel.
USES: ethyl ethanoate is used as a solvent in chromatography as well as
pineapple flavouring.
Naming; the alcohol that was added comes first i.e. ethanol + methanoic acid
will produce an ester call ethyl methanoate
Acyl chlorides and
Esters
REACTIONS OF ESTERS
Forming a polyester
Dicarboxylic acid
Diol
>
Polyester
Water
4.9
Spectroscopy and Chromatography
EM Radiation:
Wavelength:
Why:
How:
Example:
Danger:
Microwaves
1mm-1m
Heating
Radiation causes electric
field; food (also polar e.g.
fats, sugars) rotate to line
up with the field. Dryer
food with less water
content will take longer to
cook as water has polar OH+ bonds.
Cooking Microwave oven
Surgery to kill cancer
cells
Chemical industry
heating
n/a
Ultraviolet
400nm-10nm
Initiating reactions
Has enough energy to split
molecules and produce free
radicals
Mass Spectroscopy
The base peak is the 100% relative
abundance which is used to find the
RFM
M peak is caused by the whole
molecular ion which breaks up into
fragments of free radicals and
positive ions, but only the positive ion
shows up on a mass spectrometer.
The other peaks are fragment ions of
Some common RFM of fragment ions:
CH3+
C2H6+
C3H7+
OH+
CHO+
COOH+
15
29
43
17
29
45
NMR Spectroscopy
This gives you information about the structure using the idea that every atomic
nucleus (with an odd number of protons/neutrons) has a weak magnetic field due
to its nuclear spin, and applying a strong magnetic field will display accordingly.
Hydrogen is a single proton and so we can use proton NMR to find how many
hydrogens there are and how theyre arranged...
Normally protons are spinning randomly, however when you apply a STRONG
EXTERNAL MAGNETIC FIELD all the protons line up. Some protons are aligned
in the direction of the magnetic field and others are opposing it. Those opposing
it are at a higher energy level and can emit a radiowave to move to the
lower energy level. Those in the direction of the magnetic field are at a lower
energy level and can absorb a radiowave and move to a higher radiowave.
NMR measures the absorption of energy.
Protons in different environments absorb different amounts of energy; due to
them being shielded by electrons experiencing the effects of the strong magnetic
force instead.
Examples of different environments:
2
environments:
4 environments:
Magnetic Resonance
- Patient is placed in a very large magnet and irradiated with radio waves
- Hydrogen nuclei in the water in patients body interacts with the radiowaves
- Different frequencies of wave are absorbed by different densities of tissue
- A series of images can be produced by moving the beam to build a 3D image
USES: cancer/bone and joint treatment, brains studies, checking purity in
pharmaceutical industry
ADV: non invasive, X-ray would be harmful
Infrared Spectroscopy
1) IR beam goes through sample
2) IR energy is absorbed by the bonds, increasing their energy
(vibrational)
3) Different bonds in different environments absorb different
wavelengths
4) Any wavelengths that you need to know will be in the data book
USES: in the chemical industry to determine the extent of a reaction by seeing
what bonds are present
Chromatography good at separating and identifying things
Mobile phase where molecules can move i.e. liquid/gas
Stationary phase where molecules cant move i.e. solid
Gas chromatography GC