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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
5
4
3
2
1
0
time (s)

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

*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 + + 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)

(because anything to the power of

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 moldm3 -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
1
2
3

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:

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+ XThus, 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;
the relationship)
k = rate constant

(you dont have to learn this, just understand


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)
we can substitute 1/t instead of k in Arrhenius
equation and find the gradient again to find a value
EA.

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

- from solid to liquid entropy has increased

- 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) >

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:

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)
H = -315kJmol-

Info:
1

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


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

1)

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

[Note: H = -315kJmol-1 is in KILOJOULES,

= - (-315000)/298
therefore x1000]
= + 1057 JK-1mol-1
3) Find total entropy
Stotal

= Ssys + Ssurr

= -284.5 + 1057
= + 772.5 JK-1mol-1
answer]

[Note: must include sign (and units) with final

When will a reaction be spontaneous?

Total entropy must increase

+ S

= kinetically favourable (wants to react; spontaneous)

total

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
oppose the
motion!
Increase
Temperature

Where does equilibrium move and why?

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...
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!
NO EFFECT ON EQUILIBRIUM POSITION
(will affect rate)

Increase Pressure

Introduce Catalyst

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

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

because in a balanced equation, there is a 2 in front see

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
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

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;
Mole fraction of a gas in mixture =

1.25
4.75

5
19

= 1.66

Step 3) Find partial pressure;


Partial pressure of gas = 714 x

5
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.
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)

Weak acids and bases only


slightly ionise. Equilibrium is
set up with mostly reactants (to
the left)

Base
Weak
Acid
Base

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 105
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.

[H+] =

OH

Kw

1.0 x 1014
0.1

= 1.0 x 10-13 mol dm-3

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
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

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
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

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
ple

Buffer

Cells need
constant pH for
biochemical
reactions to take
place
Controlled by the
equilibrium
between
dihydrogen
phosphate and
hydrogen
phosphate
H2PO4HPO42-

Blood need to be kept at


pH 7.4

Food products changes


in pH occur due to fungi
and bacteria

Carbonic acid (H2CO3)

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-

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.
for [H+]

2. Rearranging

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,


bonds where

only occurs in double

they cannot be superimposed.


i.e. groups are

rotation

*known as

is

restricted

fixed in position.

enantiomers

The chiral carbons has four different

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

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
Bradys reagent

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

Cu2+(aq) + e- > Cu+


(aq)
Positive test = yellow precipitate
If aldehyde positive = ethanal
If ketone positive = one end is CH3

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

Ketone > Secondary alcohol

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 +
HCl

- Vigorous reaction with cold water


acyl chloride + H2O > COOH + HCl
ALCOHOL (produce ester)
- Violent reaction @298K
acyl chloride + OH > COOCH + HCl

*NOTE: HCl gas is always given off


(observation)

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:
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

Initiating reactions such as


substitution between halogen
and alkane
- Cl2 UV> 2Cl
- CF3Cl UV> CF3 + Cl
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+
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:

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