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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 -3 s -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

4

2

0 time (s)

[X]

5

4

3

2

1

0 [X]

rate

ZERO ORDER

6

4

2

0 time (s)

[X]

6

4

2

0 [X]

rate

6

4

2

0 time (s)

[X]

8

6

4

2

0 [X]

rate

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 -3 s -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 3) for each of these plots will give us the INITIAL rate of each. Compare the results e.g.
 Experiment Change compared to experiment 1 Rate of reaction Change 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) + O 3 (g) —> ClO•(g) + O 2 (g)

ClO•(g) + O•(g) —> Cl•(g) + O 2 (g)

slow rate determining step

fast reaction

Therefore, Cl• and O 3 must be in the rate equation as they are the reactants from the slowest step.

RATE = k*Cl•+*O 3 ]

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:

OR

1)

2)

X + Y > Z

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 (C δ+ ) to Halogen (X δ- ) 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 δ+ X δ-

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;

k = rate constant

T = temperature (K)

A = another constant

Some relationships to note:

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

E A = activation energy (J)

R = gas constant (8.31 JK -1 mol -1 )

 1) As E A increases, k will get smaller. Therefore large activation energy, means a slow rate – this 2) makes sense! 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 = E A /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 E A /R (m). Then R is just a number that we know (8.31 JK -1 mol -1 ) we can rearrange and find the activation energy.

EXAMPLE:

Iodine clock reaction

S 2 O 8 2- (aq) + 2I - (aq) > 2SO 4 2- (aq) + I 2 (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 E A . 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. 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: E.G. when enzymes catalyse reactions in your body, all reactants are aqueous, this is a homogenous catalysis. 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 lowest entropy. e.g. S ѳ (H 2 O (s) ) = 7.4 JK -1 mol -1 (see below) Some randomness, some entropy. e.g. S ѳ (H 2 O (l) ) = 70 JK -1 mol -1 (see below) Most randomness, highest entropy. e.g. S ѳ (H 2 O (g) ) = 189 JK -1 mol -1 (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 -1 mol -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: NaHCO 3 (s) + H + (aq) —> Na + (aq) + CO 2 (g) + H 2 O(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: ΔS sys

=

S products -

S reactants

ΔS total

=

ΔS sys +

ΔS surr

Where;

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

ΔS surr = Entropy change of a surrounding

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

 EXAMPLE: NH 3 (g) + HCl(g) —> NH 4 Cl(s) Info: ΔH = -315kJmol -1

S ѳ (NH 3(g) ) = 192.3 JK -1 mol -1

1)

Find entropy of the system

ΔS sys

=

S products -

S reactants

= 94.6 (192.3 + 186.8)

= - 284.5 JK -1 mol -1

2)

Find entropy of surroundings = - (-315000)/298

= + 1057 JK -1 mol -1

3)

Find total entropy

ΔS total

=

ΔS sys +

ΔS surr

= -284.5 + 1057

S ѳ (HCl (g) ) = 186.8 JK -1 mol -1

S ѳ (NH 4 Cl (s) ) = 94.6 JK -1 mol -1

[Note: ΔH = -315kJmol -1 is in KILOJOULES, therefore x1000]

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 NH 2 Cl(s)

Ba(OH) 2 .8H 2 O(s)

+

2NH 2 Cl(s)

>

BaCl 2 (s) +

10H 2 O(l) +

2NH 3 (g)

When you add barium hydroxide to ammonium chloride:

  Smell of ammonia gas  Temperature drops below 0˚C 2) Cold pack – NH 4 NO 3 (s) and H 2 O(l)

NH 4 NO 3 (s)

H 2 O(l)>

NH 4 + (aq) +

NO 3 - (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 ΔS surr will be negative see above equation) the ΔS sys 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 + CO 2

Kinetic inertness when the ΔS total 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, ΔH hyd the enthalpy change when 1 mole of aqueous ions is formed from gaseous ions. E.G. Na + (g) > Na + (aq)

The standard lattice enthalpy, ΔH ѳ latt 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, ΔH sol 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 ΔH ѳ latt AND ΔH hyd include;

 1) Ionic charge; = larger charge = more exothermic lattice energy = MORE NEGATIVE LATTICE ENTHALPY/ENTHALPY OF HYDRATION E.G. NaCl has ΔH ѳ latt = -780kJmol -1 whereas MgCl 2 has ΔH ѳ latt = -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;

ΔH 1 = ΔH 2 + ΔH 3

REMEMBER (for ΔH sol ): GASEOUS IONS DOWN, AQUEOUS IONS UP

Guns In Detroit, Apples In Ukraine

4.3 Equilibria

RECAP: (for exothermic reaction)

 LE CHATELIER – oppose the motion! Where does equilibrium move and why? 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

2SO 2 (g) + O 2 (g) 2SO 3 (g)

USES = fertilisers, dyes, medicines, batteries

2)

Haber process making ammonia

N 2 (g) + 3H 2 (g) 2NH 3 (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. H 2 (g) + I 2 (g) 2HI(g) Initial concentration: H 2 = 1.0moldm -3 I 2 = 1.0moldm -3 Equilibrium concentration: H 2 = 0.228moldm -3 I 2 = 0.228moldm -3

From this we can see that the ratio has remained the same, i.e. 1:1

K p / K c

What is K p / K c ?

K p / K c 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 K p 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 K p , 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:

Fe 2+ (aq) + Ag + (aq) Fe 3+ (aq) + Ag(s)

 1) Add 500cm 3 of 0.1moldm -3 silver nitrate solution to 500cm 3 of 0.1 moldm -3 of iron (II) sulfate 2) solution Leave mixture in stoppered flask at 298K, it will reach equilibrium 3) Take samples and titrate
 CALCULATION: Reactant/Product Fe 2+ (aq) Ag + (aq) Fe 3+ (aq) Ag(s) Initial concentration (moldm -3 ) 0.05 0.05 0 0 Equilibrium concentration (from titre results) 0.0439 0.0439 0.0061 solid (1:1 ratio) (0.05 – 0.0439) Equilibrium constant   Units Calculating partial pressures;  EXAMPLE:

Minty Fruits Taste Minty When 3.0 moles of PCl 5 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 Cl 2 , 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 =

=

= 1.66

Step 3) Find partial pressure;

Partial pressure of gas = 714 x

= 187.9kPa

Equilibrium and Entropy are related

S total = R lnK

When the total entropy, ∆S total, 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 = 10 5 = mostly products K = 10 10 = 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)

BrønstedLowry 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 H 2 O to form HYDROXONIUM IONS H 3 O +

*NOTE: Acid-base equilibria involves the transfer of protons, either donated or accepted.

 example reason Strong Acid HCl(g) —> H + (aq) + Cl - (aq) NaOH(s) + H 2 O(l) —> Na + (aq) + OH - (aq) Strong acids and bases ionise almost completely in water. *HCl has a pH of 0 = completely ionised Base Weak Acid Base CH 3 COOH(aq) NH 3 (aq) + H 2 O(l) CH 3 COO - (aq) + H + (aq) NH 4 + (aq) + OH - (aq) Weak acids and bases only slightly ionise. Equilibrium is set up with mostly reactants (to the left)

Conjugate acid base pairs

HA and A - are conjugate pairs

H 2 O and H 3 O + 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 K c of water is 1.0 x 10 -14 mol 2 dm -6

(We often define this with its own notation K w )

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: H 2 SO 4 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 (CH 3 CH 2 COOH). The K a of propanoic acid is 1.3 x 10 -5 moldm -3 .

K a = [H + ] 2 /[CH 3 CH 2 COOH]

[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 mol 2 dm -6

1)

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

[H + ] =

Therefore, pH = -log [1.0 x 10 -13 ]

= 13.0

=

= 1.0 x 10 -13 mol dm -3

(ph value is large expected for a strong alkali)

CALCULATION: finding the pK a

pK a = - log [K a ]

1)

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

3.75.

 3.75 = -log[K a ] K a = 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. CH 3 COOH)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 change Colour in acid alkali Methyl orange red 3.1-4.4 yellow phenolphthalein colourless 8.3-10 pink acid
alkali
pH scale

pH Curves Strong acid/Strong alkali
Phenolphthalein indicator Weak acid/Strong alkali
Phenolphthalein indicator Strong acid/Weak alkali
Methyl orange indicator Weak acid/Weak alkali

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 K a 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 pK a of the weak acid, then we can use K a = 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 CH 3 COO - Na + (aq)—> CH 3 COO - (aq) + Na + (aq) This fully dissociates; therefore mostly ethanoate ions NH 4 Cl(aq)—> NH 4 + (aq) + Cl - (aq) This fully dissociates; therefore mostly ammonium ions CH 3 COOH(aq) CH 3 COO - (aq) + H + (aq) NH 4 + (aq) H + (aq) + NH 3 (aq) This only slightly dissociates; therefore mostly ethanoic acid This only slightly dissociates; therefore mostly ammonium ADDING ACID: (small amount) [H + ] increases which combines with the CH 3 COO - to form CH 3 COOH so equilibrium shifts to left, no change in pH. ADDING ACID: (small amount) [H + ] increases which combines with the NH 3 to form NH 4 so equilibrium shifts to left, no change in pH. ADDING ALKALI: (small amount) [OH - ] increases which combines with the H + to form H 2 O which removes the H + ions from solution, so more H + dissociate from CH 3 COOH so equilibrium shifts to right, no change in pH. ADDING ALKALI: (small amount) [OH - ] increases which combines with the H + to form H 2 O which removes the H + ions from solution, so more H + dissociate from NH 4 + so equilibrium shifts to right, no change in pH.

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

 Example Cells – need constant pH for biochemical reactions to take place Blood – need to be kept at pH 7.4 Food products – changes in pH occur due to fungi and bacteria Buffer Controlled by the equilibrium between dihydrogen phosphate and hydrogen phosphate Carbonic acid (H 2 CO 3 ) Sodium citrate H 2 CO 3 H 2 O + CO 2 Citric acid citrate ions Lungs - by breathing out CO 2 , levels of H 2 CO 3 decrease and so equilibrium moves to the right Or Phosphoric acid phosphate ions H 2 PO 4 - H + + HPO 4 2- Or H 2 CO 3 H + + HCO 3 - Benzoic acid benzoate ions Kidneys control this equilibrium

CALCULATION:

A buffer solution of 0.4 moldm -3 of

1. Equation for K a

methanoic acid and 0.6 moldm -3 sodium

methanoate.

2. Rearranging for [H + ]

For methanoic acid K a = 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

mirror images of each other,

they cannot be superimposed.

*known as

enantiomers The chiral carbons has four different

groups attached to it.

They are optically active (they rotate

plane-polarised light) one will rotate

clockwise and the other anticlockwise.

E/Z

only occurs in double bonds where

rotation is restricted i.e. groups are

fixed in position.  Z-ISOMER

CIS “same” side

E-ISOMER

TRANS “opposite sides”

determined by how the heaviest

molecules are distributed around

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 δ+ X δ- ) move heterolytically to the X δ- (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 δ+ X δ- ) move heterolytically to the X δ- (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 O δ- H δ+ 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 δ+ =O δ- bond. Oxygen uses its lone pair to form hydrogen bonds with H δ+ 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. 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 + 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 Ag(NH 3 ) 2 + (aq) + e - —> Ag(s) +2NH 3 (aq) Fehlings/Benedicts Blue solution of copper(II) ions dissolved in NaOH(aq) become Cu + ions; Cu 2+ (aq) + e - —> Cu + (aq) No change Brick red precipitate (Cu + ions) Aldehyde oxidised solutions Iodine in alkali + heat (tests for CH 3 on carbon attached to oxygen) Positive test = yellow precipitate If aldehyde positive = ethanal If ketone positive = one end is CH 3

*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: [LiAlH 4 in dry ether]

Aldehyde > Primary alcohol

Carboxylic Acids Ketone > Secondary alcohol

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

They can hydrogen bond with water due to their polar C δ+ =O δ- bond. Oxygen uses its lone pair to form hydrogen bonds with H δ+ 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) CH 3 COOH + NaOH > CH 3 COONa + H 2 O

sodium ethanoate

ethanoic acid

*NOTE: CO 2 causes effervescence 2) 2CH 3 COOH + Na 2 CO 3 > 2CH 3 COONa + H 2 O + CO 2

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?

Reduction;

3NaOH + C 6 H 8 O 7 > Na 3 C 6 H 5 O 7 + 3H 2 O

1) Find moles 2) Find ratio/moles

3) Find concentration

mols = conc x vol = 0.0125 x 0.1 = 0.00125mols 3mol NaOH neutralised 1mol citric acid; 3:1 0.00125 ÷ 3 = 0.000417mol conc = mols ÷ vol 0.025 ÷ 0.000417 = 0.017 moldm -3

1) CH 3 COOH LiAlH 4 (in dry ether)> 2CH 3 OH

2) CH 3 COOH + PCl 5 > CH 3 COCl + POCl 3 + 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

WATER (produce carboxylic acid)

- Vigorous reaction with cold water

acyl chloride + H 2 O > COOH + HCl

ALCOHOL (produce ester)

- Violent reaction @298K

acyl chloride + OH > COOCH + HCl

AMMONIA (produce amide)

- Violent reaction at 298K

acyl chloride + NH 3 > CONH 2 + HCl

AMINE (produce Nsub-amide)

Violent reaction at 298K

acyl chloride + CNH 2 > CONH 2 C + HCl

*NOTE: HCl gas is always given off (observation)

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 (H 3 COO - ) 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 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 O δ- —H δ+ bonds. Has enough energy to split molecules and produce free radicals Example: Cooking – Microwave oven Surgery – to kill cancer cells Chemical industry – heating Initiating reactions such as substitution between halogen and alkane - Cl 2 —UV—> 2Cl• - CF 3 Cl —UV—> CF 3 + Cl• Danger: n/a This initiation can cause one Cl• can cause the destruction of two O 3 molecules and another Cl• Massive chain reaction.

Mass Spectroscopy Some common RFM of fragment ions:

 CH 3 + 15 C 2 H 6 + 29 C 3 H 7 + 43 OH + 17 CHO + 29 COOH + 45

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.

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(CH 3 ) 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)

2)

3)

4) IR beam goes through sample IR energy is absorbed by the bonds, increasing their energy (vibrational) Different bonds in different environments absorb different wavelengths 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 coiled tube e.g. oil Stationary phase is small particles of a 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