This is for the Unit 4 of Edexcel Chemistry A2 Level. Enjoy, and any feedback is very welcome.

4.1 Rates of Reactions

Reaction Rate = change in amount of reactants/products per unit time (units: mol dm -3s-1)

Following a reaction;

 gas volume produced (gas syringe)

 mass lost (balance)
 colour change (colorimeter)
 clock reaction (sudden change at particular time means specific concentration of product has
been reached - the shorter the time taken, the faster the rate)
 electrical conductivity (number of ions will change as reaction occurs)

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.
Shapes of Rate-Concentration Graphs tell you the order.

6 6 6
5 5 5
4 4 4
3 3 3
Column2 2 Column2 2 Column2
2
1 1 1
0 0 0
time (s) time (s) time (s)

5 6 7
4 5 6
4 5
3 4
3
2 Column2 Column2 3 Column2
2 2
1 1 1
0 0 0
[X] [X] [X]

ZERO ORDER FIRST ORDER SECOND ORDER

*square brackets indicate concentration. For example [X] = concentration of X.

Half-life = time taken for half the reactant to react

If the half life is constant = first order

If the half life is doubling = second order

You can also calculate the half life using reaction rates. For example, if you’re given the rate constant
(see below) and the order you can work out half life (you don’t need to know how, just to be aware
of it)

Rate Equations

Rate equation = tell you how the rate is affected by the concentrations of reactants.

E.G. Rate = k[A]m[B]n

Where:

m = order of A

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 + + I- (reaction occurs in acid)

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+] (because anything to the power of 0 is 1)

How to calculate rate constant from the orders and rate?

Rearrange to make k the subject and calculate.

Units of k can be found as you know concentration is moldm -3 and rate is moldm-3s-1 using a normal
“cancelling” method.

Using data to deduce the order

1) The experiment: titrate sample solutions against sodium thiosulfate and starch to work out
the concentration of the iodine. Repeat experiment, changing only the concentration for
ONE REACTANT at a time.

experiment 1 2 3 4 5 6 7
[propanone 0.4 0.8 1.2 0.4 0.4 0.4 0.4
]
[iodine] 0.002 0.002 0.002 0.004 0.006 0.002 0.002
[H+] 0.4 0.4 0.4 0.4 0.4 0.8 1.2
Here, first we changed the concentration of propanone for experiments 1, 2 and 3.

Then, we changed the concentration of iodine in experiments 4 and 5.

Lastly, we changed concentration of H + in experiments 6 and 7.

2) From this table we can plot 7 Concentration-Time graphs. Finding the gradient at time zero
for each of these plots will give us the INITIAL rate of each.
3) Compare the results e.g.

Experiment Change compared to Rate of reaction Change

experiment 1
1 --- 0.033 ---
2 [propanone] doubled 0.062 Rate doubled
3 [propanone] trebled 0.092 Rate trebled
4 [iodine] doubled 0.034 No change
5 [iodine] trebled 0.032 No change
6 [H+] doubled 0.058 Rate doubled
7 [H+] doubled 0.094 Rate trebled

*Reaction rates won’t be exactly double or treble due to experimental errors etc.
 4) Now we can work out the rate equation:

 Rate is proportional to [propanone] so the reaction is of order 1 with respect to propanone.

 Rate does not change/is independent of [iodine] so the reaction is of order 0 with respect to
iodine.
 Rate is proportional to [H+] so the reaction is of order 1 with respect to [H +].

Rate determining step = slowest step in a multi-step reaction

(if a reactant appears in the rate equation it MUST be a rate determining step including catalysts
which may appear in a rate equation)

PREDICITIONS

The order of a reaction with respect to a reactant shows the number of molecules that the reactant
is involved in with regard to the rate-determining step. EXAMPLE: rate = k[X][Y] 2. Here, one molecule
of X and 2 molecules of Y will be involved in the rate determining step.

Chlorine free radicals in the ozone consist of 2 steps:

Cl•(g) + O3(g) —> ClO•(g) + O2(g) slow rate determining step

ClO•(g) + O•(g) —> Cl•(g) + O2(g) 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, it’s
mechanism 1 which is the right one.
Halogenoalkanes – Nucleophilic Substitution (S N)

Halogenoalkanes can be hydrolysed by OH - ions by nucleophilic substitution. This is where a

nucleophile (e.g. :OH-) attacks a molecule and is swapped/substituted for one of the attached groups
(e.g. Br δ-). In this case the Carbon (Cδ+) to Halogen (Xδ-) bond is POLAR as halogens are much more
electronegative than the carbon so they draw in electrons making the Carbon slightly/delta positive.
The bond looks like this:

Cδ+ — Xδ-

Thus, the carbon can be easily attacked by a nucleophile who likes positive areas. This mechanism
occurs:

*C-Br bond breaks heterolytically (unevenly)

 Primary – react by SN2 where 2 molecules/ions are involved in the rate determining step
 Secondary – react by SN1 and SN2
 Tertiary – react by SN1 where 1 molecule/ion is involved in the rate determining step

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; (you don’t have to learn this, just understand the relationship)

k = rate constant EA = activation energy (J)

T = temperature (K) R = gas constant (8.31 JK-1mol-1)

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

(don’t forget, ln A is just a constant, a number)

This looks a bit like:

y = mx + c

If we plot ln k (y) against 1/T (x), the gradient we produce will

be –EA/R (m). Then R is just a number that we know (8.31 JK -1mol-1) we can rearrange and find the
activation energy.

EXAMPLE:

Iodine clock reaction

S2O82- (aq) + 2I- (aq) —> 2SO42- (aq) + I2 (aq)

Rate of reaction is inversely proportional to the time taken for the solution to change colour

i.e. increased rate = decreased time taken

k α 1/t

We can say that 1/t is the same as k (rate constant) and we can
substitute 1/t instead of k in Arrhenius’ equation and find the
gradient again to find a value for EA.
Catalysts

Catalyst = increases rate of a reaction by providing an alternative reaction pathway with a LOWER
activation energy (EA). 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 HETEROGENOUS 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.
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 it’s in is much bigger and the
particles can be arranged in lots of different ways.

SOLID LIQUID GAS

No randomness, therefore Some randomness, some Most randomness, highest
lowest entropy. entropy. entropy.
e.g. Sѳ (H2O(s)) = 7.4 JK-1mol-1 e.g. Sѳ (H2O(l)) = 70 JK-1mol-1 e.g. Sѳ (H2O(g)) = 189 JK-1mol-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. - from solid to liquid entropy has increased a bit

- from liquid to gas entropy has increased a lot

4. Complicated/complex molecules = more entropy

DEFINITIONS:

Standard entropy of a substance, S ѳ, is the entropy of one mole of a substance under standard
conditions of 298K and 1atm. The units are JK-1mol-1.

We expect exothermic reactions to be the spontaneous ones; however some endothermic reactions
are spontaneous too. This is to do with entropy. If entropy is high enough, the reaction will be
spontaneous, whether the reaction is exo/endothermic.

EXAMPLE:

NaHCO3(s) + H+(aq) —> Na+(aq) + CO2(g) + H2O(l)

1 mole 1 mole 1 mole 1 mole 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 ΔH – see
below)
LEARN THESE:

ΔSsys = Sproducts - Sreactants

ΔStotal = ΔSsys + ΔSsurr

Where;

ΔSsys = Entropy change of a system, the entropy change between the reactants and the products

ΔSsurr = Entropy change of a surrounding

ΔStotal = Total entropy change, the sum of the entropy changes of the system and the surroundings

EXAMPLE:

NH3(g) + HCl(g) —> NH4Cl(s)

Info: ΔH = -315kJmol-1

Sѳ (NH3(g)) = 192.3 JK-1mol-1 Sѳ (HCl(g)) = 186.8 JK-1mol-1 Sѳ (NH4Cl(s)) = 94.6 JK-1mol-1

1) Find entropy of the system

ΔSsys = Sproducts - Sreactants

= 94.6 – (192.3 + 186.8)

= - 284.5 JK-1mol-1

2) Find entropy of surroundings

= - (-315000)/298 [Note: ΔH = -315kJmol-1 is in KILOJOULES, therefore x1000]

= + 1057 JK-1mol-1

3) Find total entropy

ΔStotal = ΔSsys + ΔSsurr

= -284.5 + 1057
= + 772.5 JK-1mol-1 [Note: must include sign (and units) with final answer]
When will a reaction be spontaneous?

 Total entropy must increase

 + ΔS total = kinetically favourable (wants to react; spontaneous)

 — ΔS total = kinetically stable (will not react on its own; not spontaneous)

* You can predict ionic compound solubility using the same idea; if ΔS 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)

When you add barium hydroxide to ammonium chloride:

 Smell of ammonia gas

 Temperature drops below 0˚C

2) Cold pack – NH4NO3(s) and H2O(l)

NH4NO3(s) —H2O(l)—> NH4+(aq) + NO3-(aq)

When you dissolve ammonium nitrate crystals in water:

Looking at the states in both these experiments, we have an INCREASE in entropy (from solids to
liquids/aqueous). These reactions are spontaneous EVEN THOUGH the ΔS surr is negative (because if
ΔH is positive for endothermic reactions the equation of ΔS surr means the overall ΔSsurr will be
negative – see above equation) the ΔSsys is GREAT ENOUGH to overcome it, meaning ΔS total will be
positive still.

DEFINITIONS:

Thermodynamic stability – where the ΔS total is negative, at RTP, the reaction will simply not occur.
E.G. limestone –> CaO + CO2

Kinetic inertness – when the ΔStotal 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, ΔHhyd – the enthalpy change when 1 mole of aqueous ions is
formed from gaseous ions. E.G. Na+(g) —> Na+(aq)

The standard lattice enthalpy, ΔHѳlatt – 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, ΔHsol – 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 ΔHѳlatt AND ΔHhyd include;

1) Ionic charge; = larger charge

= more exothermic lattice energy
= MORE NEGATIVE LATTICE ENTHALPY/ENTHALPY OF HYDRATION

E.G. NaCl has ΔHѳlatt = -780kJmol-1 whereas MgCl2 has ΔHѳlatt = -2526kJmol-1 because
magnesium has a charge of 2+ which is greater than sodium’s 1+

2) Ionic radii; = smaller ionic radii

= more exothermic lattice enthalpy
= higher charge density
= MORE NEGATIVE LATTICE ENTHALPY/ENTHALPY OF HYDRATION

E.G. Sodium’s ionic radius is bigger than magnesium’s (because Mg has one more proton
which has a stronger positive nuclear attraction to its electrons – see unit 1/2) therefore
magnesium will have a more negative lattice enthalpy/hydration enthalpy.

Finding the enthalpy of solution

where we use a similar principle to Hess’ Law;

ΔH1 = ΔH2 + ΔH3

REMEMBER (for ΔHsol ): GASEOUS IONS DOWN, AQUEOUS IONS UP

Guns In Detroit, Apples In Ukraine

4.3 Equilibria
RECAP: (for exothermic reaction)

LE CHATELIER – oppose Where does equilibrium move and why?

the motion!
Increase Temperature Toward reactants, therefore less products; Move to the endothermic
side. Higher kinetic energy so more chance of successful collision
LOW temp = high yield = but slow process...
Increase Pressure Toward side with less molecules of gas (only affects gases). Particles are
pushed together, which increases chances of successful collision.
HIGH pressure = high yield = expensive!
Introduce Catalyst NO EFFECT ON EQUILIBRIUM POSITION
(will affect rate)

At equilibrium the amount of reactants and products is the SAME.

Dynamic Equilibrium – a reaction that occurs in both ways at the same time (conditions; in a closed
system at constant temperature)

Many industrial reactions are reversible; we use this sign for equilibria:

E.G. Both these experiments are good economically

1) Contact process – making sulphuric acid

2SO2(g) + O2(g) 2SO3(g)

USES = fertilisers, dyes, medicines, batteries

2) Haber process – making ammonia

N2(g) + 3H2(g) 2NH3(g)

USES = fertilisers, producing nitrogen-based compounds

EXPERIMENT: Hydrogen-Iodine Reaction (REVERSIBLE)

There is a relationship between the concentration of initial reactants/products and the equilibrium
concentrations which are produced from them

E.G. H2(g) + I2(g) 2HI(g)

Initial concentration: H2 = 1.0moldm-3 I2 = 1.0moldm-3

Equilibrium concentration: H2 = 0.228moldm-3 I2 = 0.228moldm-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 2 because in a balanced equation, there is a 2 in front – see below

E.G. 4X 2Y + 3Z

*We can calculate Kp using partial pressures (see below)

As long as the equilibrium is HOMOGENOUS (all reactants/products in the same state) then we can
use this general rule for finding Kc;

If the equilibrium is HETEROGENOUS (where reactants/products are in

different states) then you must LEAVE OUT any concentrations that are
solid.

For Kp, HOMOGENOUS equilibriums can be calculated using;

If the equilibrium is HETEROGENOUS then you only take into account

the gases.

*Note: we dont use square brackets for equilibrium partial pressures

EXPERIMENT: Fe2+(aq) + Ag+(aq) Fe3+(aq) + Ag(s)

1) Add 500cm3 of 0.1moldm-3 silver nitrate solution to 500cm3 of 0.1 moldm-3 of iron (II) sulfate
solution
2) Leave mixture in stoppered flask at 298K, it will reach equilibrium
3) Take samples and titrate
CALCULATION:

Reactant/Product Fe2+(aq) Ag+(aq) Fe3+(aq) Ag(s)

Initial concentration 0.05 0.05 0 0
(moldm-3)
Equilibrium concentration 0.0439 0.0439 0.0061 solid
(from titre results) (1:1 ratio) (0.05 – 0.0439)
Equilibrium constant

Units

Calculating partial pressures;

Minty Fruits Taste Minty

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 PCl 5?

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;

1.25 5
Mole fraction of a gas in mixture = = = 1.66
4.75 19

Step 3) Find partial pressure;

5
Partial pressure of gas = 714 x = 187.9kPa
19
Equilibrium and Entropy are related

∆Stotal = R lnK
When the total entropy, ∆Stotal, increases, the equilibrium constant, K, will also increase.

If; K = 10-10 = reaction will not occur

K = 10-5 = mostly reactants

K = 1 = balanced products and reactants

K = 105 = mostly products

K = 1010 = reaction complete

4.7 Acid/base Equilibria

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)

Brønsted–Lowry 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.

example reason
Strong Acid HCl(g) —> H+(aq) + Cl-(aq) Strong acids and bases ionise almost
Base NaOH(s) + H2O(l) —> Na+(aq) + OH-(aq) completely in water.
*HCl has a pH of 0 = completely ionised
Weak Acid CH3COOH(aq) CH3COO-(aq) + H+(aq) Weak acids and bases only slightly
Base NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) ionise. Equilibrium is set up with
mostly reactants (to the left)

Conjugate acid base pairs

 HA and A- are conjugate pairs

 H2O and H3O+ are conjugate pairs

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;

At 298K/1atm, the Kc of water is 1.0 x 10-14 mol2dm-6

(We often define this with its own notation – Kw)

Kw = Kc x [H2O] = the ionic product of water = [H +][OH-] with UNITS: mol2dm-6

pH – “power of hydrogen” - is a measure of the hydrogen ion concentration

pH = - log [H+]
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 (pH value is small – expected for a strong 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 isn’t as straight forward as above. Another constant called K a
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 10-5 moldm-3.

Ka = [H+]2/[CH3CH2COOH]

[H+] = 5.09 x 10-4

pH = -log[5.09 x 10-4]

pH = 3.29
 CALCULATION: finding the pH of a strong base

One OH- ion fully dissociates per mole of base so the concentration of OH - ions and concentration of
the base is the same. However to work out pH from the formula, we need [H +]. Therefore, we use
our knowledge of (@ 298K), Kw = 1.0 x 10-14 mol2dm-6

1) Find the pH of 0.1 moldm-3 of NaOH at 298K.

[H+] =
Kw = 1.0 x 10−14 = 1.0 x 10-13 mol dm-3
¿¿ 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 [Ka]

1) Calculate the pH of 0.05moldm-3 of methanoic acid (HCOOH). Methanoic acid has a pK a of
3.75.

3.75 = -log[Ka] Ka = 1.78 x 10-4

1.78 x 10-4 = [H+]2/[0.05] [H+] = 2.98 x 10-3

pH = -log[2.98 x 10-3] pH = 2.53

Lastly, you should be aware that;

 diluting a strong acid (e.g. HCl) by a factor of 10 increases the pH by 1

 diluting a weak acid (e.g. CH3COOH)by a factor of 10 increases the pH by 0.5

1) add a measure of acid (with known concentration) to

burette
2) rough titration; swirl conical flask for approximate end
point*
3) accurate titration; drop by drop
4) record amount of base needed to neutralise the acid
5) Repeat for more accurate readings

*end point: when the solution changes colour (also known as

equivalence point – see below)

INDICATORS

Indicator Colour in pH when colour Colour in

acid change alkali
Methyl orange red 3.1-4.4 yellow
 phenolphthalei colourless 8.3-10 pink
n
pHacid
scale alkali

pH Curves

Strong acid/Strong alkali Strong acid/Weak alkali

Phenolphthalein indicator Methyl orange indicator

Weak acid/Strong alkali 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

The half equivalence point is the

point where half the acid has been
neutralised, where half the volume
of strong base has been added the
weak acid before equivalence.

At the half equivalence point [HA] = [A-]

Therefore;
 Thus, we can say that the half equivalence point is also
the pKa of the weak acid, then we can use Ka = 10-pKa
Buffers

- RESIST changes in pH when small amounts of acid/alkali are added

- Doesn’t stop the pH from changing completely
- They only work when small amounts of acids/alkalis are added

ACIDIC BUFFERS ALKALINE BUFFERS

Weak acid + Salt Weak base + Salt
CH3COO-Na+(aq)—> CH3COO-(aq) + Na+(aq) NH4Cl(aq)—> NH4+(aq) + Cl -(aq)
This fully dissociates; therefore mostly This fully dissociates; therefore mostly
ethanoate ions ammonium ions

CH3COOH(aq) CH3COO-(aq) + H+(aq) NH4+(aq) H+(aq) + NH3(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.
This only slightly dissociates; therefore mostly
ammonium
ADDING ACID: (small amount)
[H+] increases which combines with the NH 3 to
form NH4 so equilibrium shifts to left, no change in
pH.

ADDING ALKALI: (small amount) ADDING ALKALI: (small amount)

[OH-] increases which combines with the H+ to [OH-] increases which combines with the H+ to
form H2O which removes the H+ ions from form H2O which removes the H+ ions from
solution, so more H+ dissociate from CH3COOH solution, so more H+ dissociate from NH4+ so
so equilibrium shifts to right, no change in pH. equilibrium shifts to right, no change in pH.

Biological environments (don’t need to learn but be aware of)

Exampl Cells – need constant Blood – need to be kept at pH 7.4 Food products – changes in pH
e pH for biochemical occur due to fungi and
reactions to take place bacteria
Buffer Controlled by the Carbonic acid (H2CO3) Sodium citrate
equilibrium between
dihydrogen phosphate H2CO3 H2O + CO2 Citric acid citrate ions
and hydrogen Lungs - by breathing out CO2, Or
phosphate levels of H2CO3 decrease and so Phosphoric acid phosphate
equilibrium moves to the right ions
H2PO4- H+ + HPO42- Or
H2CO3 H+ + HCO3- Benzoic acid benzoate ions
Kidneys control this equilibrium
CALCULATION:

A buffer solution of 0.4 moldm-3 of 1. Equation for Ka

methanoic acid and 0.6 moldm-3 sodium

methanoate. 2. Rearranging for [H+]

For methanoic acid Ka= 1.6 x 10-4 moldm-3.

What is the pH of the buffer? 3. Find pH

4.8 Further Organic Chemistry
Isomers

Structural: compounds with the same molecular formulae but different structural formulae

Stereoisomerism: Optical E/Z

mirror images of each other, only occurs in double bonds where

they cannot be superimposed. rotation is restricted i.e. groups are

*known as fixed in position.

enantiomers

The chiral carbons has four different Z-ISOMER E-ISOMER

groups attached to it. CIS “same” side TRANS “opposite sides”

They are optically active (they rotate determined by how the heaviest

plane-polarised light) – one will rotate molecules are distributed around

clockwise and the other anticlockwise. the double bond.

A racemic mixture contains equal quantities of each enantiomer

of an optically active compound (rotates plane polarised light).

Optical Activity can be used to work out a reaction mechanism. For example, nucleophillic
substitution can occur in two different ways;

If a reaction is SN1 and you start with one enantiomer, the product will be a racemic mixture of two
optical isomers. The electrons move in the polar bond (Cδ+ — Xδ-) move heterolytically to the Xδ- (1
stage)

If a reaction is SN2 and you start with one enantiomer, the product will be a single enantiomer which
will rotate the polarised light. First the nucleophile attacks a carbon and then the electrons in the
polar bond (Cδ+ — Xδ-) move heterolytically to the Xδ- (2 stages)

*Remember: from rates of reaction; SN1 means only 1 molecule will be involved in the rate
determining step and SN2 means there are 2 molecules in the rate determining step
 Aldehydes and Ketones

They do not hydrogen bond with themselves as they don’t have a polar Oδ-
—Hδ+ bond. For this reason, aldehydes and ketones have lower boiling points than alcohols (which

They can hydrogen bond with water due to their polar Cδ+=Oδ- bond. Oxygen uses its lone pair to
form hydrogen bonds with Hδ+ atoms on the water molecules.

Note: small ketones/Aldehydes will dissolve due to the polarity mentioned above, however large
ketones/Aldehydes will have very strong intermolecular forces and will not dissolve.

NUCLEOPHILIC ADDITION

Hydrogen cyanide is a weak acid – it partially dissociates in water

HCN H+ + CN-

CN- is a nucleophile and attacks the slightly positive carbon atom and
donates its electrons to it. The electrons in the C=O bond move to
the oxygen. H+ from water/hydrogen cyanide bond to the oxygen
forming OH.

NOTE: HCN is a very toxic gas; acidified potassium cyanide is used to reduce the risk. Experiment
must be conducted in fume cupboard.

Evidence of optical activity: carbonyl group is planar; nucleophile can attack from either side.
Asymmetric (not symmetrical) ketone/aldehyde + CN - —> racemic mixture/two optical isomers.
This is what you expect if the CN can attack either side, producing two different isomers.

Tests to identify

TEST Info Ketone Aldehyde

Bradys reagent 2,4-dinitropheylhydrazine Orange Orange

Tollen’s reagent Colourless solution of silver No change Silver mirror

+ heat (water bath – not nitrate dissolved in ammonia (Ag(s))
flame as flammable!) which gets reduced and Aldehyde oxidised
changes colour;

Ag(NH3)2+(aq) + e- —> Ag(s)

+2NH3 (aq)
Fehlings/Benedicts Blue solution of copper(II) No change Brick red precipitate
solutions ions dissolved in NaOH(aq) (Cu+ ions)
become Cu+ ions; Aldehyde oxidised

Cu2+(aq) + e- —> Cu+(aq)

Iodine in alkali + heat Positive test = yellow precipitate
(tests for CH3 on carbon If aldehyde positive = ethanal
attached to oxygen) If ketone positive = one end is CH3
*NOTE: Brady’s: 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 Ketone —> Secondary alcohol

Carboxylic Acids

They hydrogen bond with themselves as they do have a polar Oδ-—Hδ+ bond. For this
reason, carboxylic acids have very high boiling points.

They can hydrogen bond with water due to their polar Cδ+=Oδ- bond. Oxygen uses its lone pair to
form hydrogen bonds with Hδ+ 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: when a molecule hydrogen bonds with just one other molecule, increasing
the size and intermolecular forces of the molecule, meaning the boiling
point is also higher.

Making a carboxylic acid:

1) Primary alcohol – oxidised – aldehyde – oxidised – carboxylic acid

2) Nitrile – hydrolysed (reflux with HCl then distil) – distilled product is carboxylic acid

REACTIONS OF CARBOXYLIC ACIDS:

Neutralisation; 1) CH3COOH + NaOH —> CH3COONa + H2O

ethanoic acid sodium ethanoate
*NOTE: CO2 causes 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 80˚C, 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 ACYL CHLORIDES REACTIONS OF ESTERS

WATER (produce carboxylic acid) Acid hydrolysis – adding water so that the
ester splits into an acid and an alcohol
- Vigorous reaction with cold water (reverse of making ester) using
acyl chloride + H2O —> COOH + HCl reflux/heat/acid catalyst.
ALCOHOL (produce ester) Base Hydrolysis
- Violent reaction @298K Reflux an ester with DILUTE ALKALI (e.g.
acyl chloride + OH —> COOCH + HCl NaOH) producing a carboxylate ion (H 3COO-)
AMMONIA (produce amide) and an alcohol.
USES: making soaps; hydrolysing vegetable
- Violent reaction at 298K oils and animal fats (trimesters) and heating
acyl chloride + NH3 —> CONH2 + HCl them with NaOH produces glycerol (tri-ol) and
sodium salt (soap) that we use every day
AMINE (produce Nsub-amide)
Trans-Esterification (TE)
Violent reaction at 298K
Hydrogenation: adding hydrogen to remove
acyl chloride + CNH2 —> CONH2C + HCl
the double bonds.
Use: making low fat spread from butter,
biodiesel
*NOTE: HCl gas is always given off Problem: some trans isomers have been
(observation) linked to various diseases
Solution: to hydrogenation:
trans-esterification;
Ester + Alcohol —> New ester

Forming a polyester

Dicarboxylic acid + Diol —> Polyester + Water

4.9 Spectroscopy and Chromatography

EM Radiation: Microwaves Ultraviolet

Wavelength: 1mm-1m 400nm-10nm
Why: Heating Initiating reactions
How: Radiation causes electric field; Has enough energy to split molecules
food (also polar e.g. fats, sugars) and produce free radicals
rotate to line up with the field.
Dryer food with less water
content will take longer to cook
as water has polar Oδ-—Hδ+
bonds.
Example: Cooking – Microwave oven Initiating reactions such as substitution
Surgery – to kill cancer cells between halogen and alkane
Chemical industry – heating - Cl2 —UV—> 2Cl•

- CF3Cl —UV—> CF3 + Cl•

Danger: n/a This initiation can cause one Cl• can
cause the destruction of two O3
molecules and another Cl•
Massive chain reaction.

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 a broken

ethanol molecule. See below.

Some common RFM of fragment ions:

CH3+ 15
C2H6+ 29
C3H7+ 43
OH+ 17
CHO+ 29
COOH+ 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 they’re 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:

Chemical shift – is the difference in absorption of a proton

relative to TetraMethylSilane (Si(CH3)4).

Where δ = 0 is the value of TMS.

Each peak = one environment. In the graph opposite,
there are two environments (2 peaks)

The less shielded a proton is, the further left the shift will be.

Spin-spin coupling – in high res, the peaks of an NMR usually split into smaller peaks, this is because
the magnetic field of neighbouring protons interact. The peaks follow an n+1 rule whereby;

2 splits [doublet] = 1 neighbouring proton (or hydrogen)

3 splits [triplet] = 2 neighbouring protons (or hydrogens)
4 splits [quartet] = 3 neighbouring protons (or hydrogens)
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 can’t move i.e. solid

Gas chromatography GC High performance liquid chromatography HPLC

Stationary phase is a viscous liquid in a long Stationary phase is small particles of a solid
coiled tube e.g. oil packed into a tube e.g. silica
Tube is built into an oven Tube is not heated
Sample injected and vaporised Sample forced through tube by high pressure
Both rely on different amounts of the sample being moved from the top of the tube to the bottom
known as the “retention time”
ADV of HPLC over GC: HPLC can be used if sample is heat sensitive or has a high boiling point