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 Column 3 Column 3 Column
2 2 2 2 2 2
1 1 1
0 0 0
time (s) time (s) time (s)

5 6
4 5
4
3
Column 3 Column
2
2 2 2
1 1
0 0
[X] [X]

10
5
Column2
0
[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 youre
given the rate constant (see below) and the order you can work out half life (you
dont 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-
3 -1
s 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.

experime 1 2 3 4 5 6 7
nt
[propano 0.4 0.8 1.2 0.4 0.4 0.4 0.4
ne]
[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 Rate of reaction Change

to experiment 1
1 --- 0.033 ---
2 [propanone] 0.062 Rate doubled
doubled
3 [propanone] 0.092 Rate trebled
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 wont 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, its 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 -). In this case the Carbon (C+) to
Halogen (X-) 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:

C+ X-

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 dont 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

(dont 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 E A/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 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 (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 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 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 JK- e.g. S (H2O(l)) = 70 JK- e.g. S (H2O(g)) = 189 JK-
1
mol-1 1
mol-1 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. - 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, 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 H see below)

LEARN THESE:

Ssys = Sproducts -

Stotal = Ssys +
Ssurr
Where;

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

Ssurr = Entropy change of a surrounding

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

EXAMPLE:

NH3(g) + HCl(g) > NH4Cl(s)

Info: H = -315kJmol-
1

S (NH3(g)) = 192.3 JK-1mol-1 S (HCl(g)) = 186.8 JK-1mol-1 S

(NH4Cl(s)) = 94.6 JK-1mol-1

1) Find entropy of the system

Ssys = Sproducts - Sreactants

= 94.6 (192.3 + 186.8)

= - 284.5 JK-1mol-1

2) Find entropy of surroundings

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

= + 1057 JK-1mol-1

3) Find total entropy

Stotal = Ssys + Ssurr

= -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

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

S total = kinetically stable (will not react on its own; not spontaneous)

* 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)

When you add barium hydroxide to ammonium chloride:

Smell of ammonia gas

Temperature drops below 0C

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 Ssurr is negative (because if H is positive for endothermic
reactions the equation of Ssurr means the overall Ssurr will be negative see
above equation) the Ssys is GREAT ENOUGH to overcome it, meaning Stotal will
be positive still.

DEFINITIONS:

Thermodynamic stability where the Stotal is negative, at RTP, the reaction will
simply not occur. E.G. limestone > CaO + CO 2
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;= smaller ionic radii

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

E.G. Sodiums ionic radius is bigger than magnesiums (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;

H1 = H2 + H3
REMEMBER (for Hsol ): GASEOUS IONS DOWN, AQUEOUS IONS UP
Guns In Detroit, Apples In Ukraine
4.3 Equilibria
RECAP: (for exothermic reaction)

LE CHATELIER Where does equilibrium move and why?

oppose the
motion!
Increase Toward reactants, therefore less products; Move to the
Temperature 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;

2
*Note: products are 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 K c;

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 0.0439 0.0439 0.0061 solid
concentration (1:1 ratio) (0.05
(from titre results) 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 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;

1.25 5
Mole fraction of a gas in mixture = 4.75 = 19 = 1.66
Step 3) Find partial pressure;

5
Partial pressure of gas = 714 x 19 = 187.9kPa
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)

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.

example reason
Strong HCl(g) > H+(aq) + Cl-(aq) Strong acids and bases ionise
Acid NaOH(s) + H2O(l) > Na+(aq) + almost completely in water.
OH-(aq) *HCl has a pH of 0 =
Base completely ionised

Weak CH3COOH(aq) CH3COO-(aq) + Weak acids and bases only

Acid H+(aq) slightly ionise. Equilibrium is
NH3(aq) + H2O(l) NH4+(aq) + set up with mostly reactants (to
Base OH-(aq) 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
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 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 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), K w = 1.0 x
10-14 mol2dm-6

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

OH
1.0 x 1014
[H+] = = = 1.0 x 10-13 mol dm-3
Kw 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

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 in
acid colour alkali
change
Methyl red 3.1-4.4 yellow
orange
phenolphthal colourles 8.3-10 pink
ein s
acid
pH
scalealkali
pH Curves

Strong acid/Strong Strong acid/Weak

alkali alkali

Phenolphthalein Methyl orange

indicator indicator

Weak acid/Strong Weak acid/Weak

alkali 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
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

- Doesnt stop the pH from changing completely
- They only work when small amounts of acids/alkalis are added

ACIDIC BUFFERS ALKALINE 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.
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
ADDING ACID: (small amount)
[H+] increases which combines with the
NH3 to form NH4 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 NH4+ so equilibrium shifts to right,
no change in pH.

Biological environments (dont need to learn but be aware of)

Exam Cells need Blood need to be kept at Food products changes

ple constant pH for pH 7.4 in pH occur due to fungi
biochemical and bacteria
reactions to take
place
Buffer Controlled by the Carbonic acid (H2CO3) Sodium citrate
equilibrium
between H2CO3 H2O + CO2 Citric acid citrate ions
dihydrogen Lungs - by breathing out Or
phosphate and CO2, levels of H2CO3 Phosphoric acid
hydrogen decrease and so phosphate ions
phosphate equilibrium moves to the Or
right Benzoic acid
H2PO4- H+ + benzoate ions
HPO42- H2CO3 H+ + HCO3-
 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
(C+ X-) move heterolytically to the X- (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 (C+ X-) move
heterolytically to the X- (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 dont have a

polar O-H+ bond. For this reason, aldehydes and ketones have lower boiling
points than alcohols (which can hydrogen bond)

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.

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- Orange Orange
dinitropheylhydrazine

Tollens reagent Colourless solution of No change Silver mirror

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

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

Cu2+(aq) + e- > Cu+

(aq)
Iodine in alkali + Positive test = yellow precipitate
heat If aldehyde positive = ethanal
(tests for CH3 on If ketone positive = one end is CH3
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 Ketone > Secondary 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: 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 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 ACYL CHLORIDES AMINE (produce Nsub-amide)

WATER (produce carboxylic acid) Violent reaction at 298K

acyl chloride + CNH2 > CONH2C +
- Vigorous reaction with cold water HCl
acyl chloride + H2O > COOH + HCl

ALCOHOL (produce ester)

*NOTE: HCl gas is always given off
- Violent reaction @298K (observation)
acyl chloride + OH > COOCH + HCl

AMMONIA (produce amide)

- Violent reaction at 298K

acyl chloride + NH3 > CONH2 + HCl REACTIONS OF ESTERS
Acid hydrolysis adding water so
that the ester splits into an acid and
an alcohol (reverse of making ester)
using reflux/heat/acid catalyst.
Base Hydrolysis
Reflux an ester with DILUTE ALKALI
(e.g. NaOH) producing a carboxylate
ion (H3COO-) and an alcohol.
USES: making soaps; hydrolysing
vegetable oils and animal fats
(trimesters) and heating them with
NaOH produces glycerol (tri-ol) and
sodium salt (soap) that we use every
day
Trans-Esterification (TE)
Hydrogenation: adding hydrogen
to remove the double bonds.
Use: making low fat spread from
butter, biodiesel
Problem: some trans isomers have
been 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 Has enough energy to split
field; food (also polar e.g. molecules and produce free
fats, sugars) rotate to line radicals
up with the field. Dryer
food with less water
content will take longer to
cook as water has polar O-
H+ bonds.
Example: Cooking Microwave oven Initiating reactions such as
Surgery to kill cancer substitution between halogen
cells and alkane
Chemical industry - Cl2 UV> 2Cl
heating
- 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

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 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:

Chemical shift is the difference in absorption of a proton

relative to TetraMethylSilane (Si(CH3)4).

Where = 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 cant move i.e. solid

Gas chromatography GC High performance liquid

chromatography HPLC
Stationary phase is a viscous liquid in a Stationary phase is small particles of a
long coiled tube e.g. oil solid 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