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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 4 2 0 time (s) [X] 6 4 2 0 time (s) [X] 6 4 2 0 time (s) [X]

5 4 3 2 1 0 [X]

6 4 rate 2 0 [X] rate

8 6 4 2 0 [X] rate




*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-3s-1 using a normal cancelling method. Using data to deduce the order 1) The experiment: titrate sample solutions against sodium thiosulfate and starch to work out the concentration of the iodine. Repeat experiment, changing only the concentration for ONE REACTANT at a time. experiment 1 2 3 4 5 6 [propanone] 0.4 0.8 1.2 0.4 0.4 0.4 [iodine] 0.002 0.002 0.002 0.004 0.006 0.002 + [H ] 0.4 0.4 0.4 0.4 0.4 0.8 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 4 5 6 7 Change compared to experiment 1 --[propanone] doubled [propanone] trebled [iodine] doubled [iodine] trebled [H+] doubled [H+] doubled Rate of reaction 0.033 0.062 0.092 0.034 0.032 0.058 0.094 Change --Rate doubled Rate trebled No change No change Rate doubled Rate trebled 7 0.4 0.002 1.2

*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) ClO(g) + O(g) > Cl(g) + O2(g) slow rate determining step 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 (SN) 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; k = rate constant T = temperature (K) A = another constant Some relationships to note:

(you dont have to learn this, just understand the relationship) EA = activation energy (J) R = gas constant (8.31 JK-1mol-1)

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 EA/R (m). Then R is just a number that we know (8.31 JK-1mol-1) we can rearrange and find the activation energy. EXAMPLE: Iodine clock reaction S2O82- (aq) + 2I- (aq) > 2SO42- (aq) + I2 (aq) Rate of reaction is inversely proportional to the time taken for the solution to change colour i.e. increased rate = decreased time taken k 1/t We can say that 1/t is the same as k (rate constant) and we can substitute 1/t instead of k in Arrhenius equation and find the gradient again to find a value for EA.

Catalysts Catalyst = increases rate of a reaction by providing an alternative reaction pathway with a LOWER activation energy (EA). A catalyst will be chemically unchanged at the end of a reaction. Adv: Small amount needed to catalyse a lot of reactions, also they are remade, thus reusable. Disadv: High specificity to the reactions they catalyse. There are two types of catalysts: HOMOGENOUS CATALYSTS 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, therefore Some randomness, some Most randomness, highest lowest entropy. entropy. entropy. e.g. S (H2O(s)) = 7.4 JK-1mol-1 e.g. S (H2O(l)) = 70 JK-1mol-1 e.g. S (H2O(g)) = 189 JK-1mol-1 (see below) (see below) (see below) *Note that zero entropy will only occur in a perfectly ordered crystal Affecting Factors: 1. More quanta (packets of energy) = More ways to arrange particles = More entropy 2. More particles = More arrangements = More entropy. E.G. X -> 2Y 2 moles of Y produced from 1 mole of X therefore entropy has increased 3. Increase in temperature = Increase in energy = More entropy E.G. - from solid to liquid entropy has increased a bit - from liquid to gas entropy has increased a lot

4. Complicated/complex molecules = more entropy DEFINITIONS: Standard entropy of a substance, S, 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) 1 mole Solid + H+(aq) > 1 mole aqueous ions Na+(aq) 1 mole aqueous ions + CO2(g) + 1 mole gas H2O(l) 1 mole 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)


Ssys = Sproducts - Sreactants 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) Info: S (NH3(g)) = 192.3 JK-1mol-1 S (HCl(g)) = 186.8 JK-1mol-1 + HCl(g) > NH4Cl(s) H = -315kJmol-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 = + 1057 JK-1mol-1 3) Find total entropy Stotal = Ssys + Ssurr = -284.5 + 1057 = + 772.5 JK-1mol-1

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

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

When will a reaction be spontaneous? Total entropy must increase

+ S


= kinetically favourable (wants to react; spontaneous)

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

* You can predict ionic compound solubility using the same idea; if Stotal 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 + CO2 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. Initial concentration: Equilibrium concentration: H2(g) + I2(g) H2 = 1.0moldm-3 H2 = 0.228moldm-3 2HI(g) I2 = 1.0moldm-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 Kc will be; *Note: products are 2 because in a balanced equation, there is a 2 in front see below E.G. 4X 2Y + 3Z

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

As long as the equilibrium is HOMOGENOUS (all reactants/products in the same state) then we can use this general rule for finding Kc; If the equilibrium is HETEROGENOUS (where reactants/products are in different states) then you must LEAVE OUT any concentrations that are solid. For Kp, HOMOGENOUS equilibriums can be calculated using; If the equilibrium is HETEROGENOUS then you only take into account the gases. *Note: we dont use square brackets for equilibrium partial pressures


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 0.0439 Ag+(aq) 0.05 0.0439 (1:1 ratio) Fe3+(aq) 0 0.0061 (0.05 0.0439) Ag(s) 0 solid


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 PCl3 and so (3 - 1.75) will leave us with the moles at equilibrium for PCl5 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 = Step 3) Find partial pressure; Partial pressure of gas = 714 x = 187.9kPa = = 1.66

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


Acid Base 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 [H+]
CALCULATION: finding the pH of a strong acid 1) Calculate the pH of 0.05 moldm-3 of nitric acid. pH = - log[H+] pH = - log[0.05] = 1.3 (pH value is small expected for a strong acid)

2) An acid has a pH of 2.45, what is the hydrogen ion concentration? pH = - log[H+] [H+] = 10-pH = 3.55 x 10-3 moldm-3 *NOTE: H2SO4 dissociates to give 2[H+] and you will have to divide the final answer by 2 to find your hydrogen ion concentration CALCULATION: finding the pH of a weak acid Weak acids do not fully dissociate so it 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), Kw = 1.0 x 10-14 mol2dm-6 1) Find the pH of 0.1 moldm-3 of NaOH at 298K. [H+] = = = 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 [Ka]

1) Calculate the pH of 0.05moldm-3 of methanoic acid (HCOOH). Methanoic acid has a pKa of 3.75. 3.75 = -log[Ka] 1.78 x 10-4 = [H+]2/[0.05] pH = -log[2.98 x 10-3] 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 Ka = 1.78 x 10-4 [H+] = 2.98 x 10-3 pH = 2.53

1) 2) 3) 4) 5)

add a measure of acid (with known concentration) to burette rough titration; swirl conical flask for approximate end point* accurate titration; drop by drop record amount of base needed to neutralise the acid 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 acid change Methyl orange red 3.1-4.4 phenolphthalein colourless 8.3-10 acid pH scale

Colour in alkali yellow pink alkali

pH Curves Strong acid/Strong alkali Strong acid/Weak alkali

Phenolphthalein indicator

Methyl orange indicator

Weak acid/Strong alkali

Weak acid/Weak alkali

Phenolphthalein indicator

Equivalence point = where a tiny amount of alkali causes a sudden big change in pH, where the acid is JUST neutralised. Equivalence point will vary depending on acid/alkali used. For the last graph between a weak acid and weak alkali, a pH meter is the best thing to use to find the equivalence point as the colour change is gradual and unclear. CALCULATION: finding the Ka of a weak acid using a pH curve

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

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

Buffers RESIST changes in pH when small amounts of acid/alkali are added Doesnt stop the pH from changing completely They only work when small amounts of acids/alkalis are added 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.

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.

Biological environments (dont need to learn but be aware of) Example Cells need constant pH for biochemical reactions to take place Buffer Controlled by the equilibrium between dihydrogen phosphate and hydrogen phosphate H2PO4H+ + HPO42Blood need to be kept at pH 7.4 Food products changes in pH occur due to fungi and bacteria Sodium citrate Citric acid citrate ions Or Phosphoric acid phosphate ions Or Benzoic acid benzoate ions

Carbonic acid (H2CO3) H2CO3 H2O + CO2 Lungs - by breathing out CO2, levels of H2CO3 decrease and so equilibrium moves to the right H2CO3 H+ + HCO3Kidneys control this equilibrium

CALCULATION: A buffer solution of 0.4 moldm-3 of methanoic acid and 0.6 moldm-3 sodium methanoate. For methanoic acid Ka= 1.6 x 10-4 moldm-3. What is the pH of the buffer? 3. Find pH 2. Rearranging for [H+] 1. Equation for Ka

4.8 Further Organic Chemistry

Isomers Structural: compounds with the same molecular formulae but different structural formulae Stereoisomerism: Optical E/Z only occurs in double bonds where rotation is restricted i.e. groups are fixed in position.

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.

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+ 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 Tollens reagent + heat (water bath not flame as flammable!) Info 2,4-dinitropheylhydrazine Colourless solution of silver nitrate dissolved in ammonia which gets reduced and changes colour; Ag(NH3)2+(aq) + e- > Ag(s) +2NH3 (aq) Blue solution of copper(II) ions dissolved in NaOH(aq) become Cu+ ions; Ketone Orange No change Aldehyde Orange Silver mirror (Ag(s)) Aldehyde oxidised

Fehlings/Benedicts solutions

No change

Brick red precipitate (Cu+ ions) Aldehyde oxidised

Cu2+(aq) + e- > Cu+(aq) Iodine in alkali + heat Positive test = yellow precipitate (tests for CH3 on carbon If aldehyde positive = ethanal attached to oxygen) If ketone positive = one end is CH3 *NOTE: Bradys: you can identify carbonyl compounds by the melting point of the orange precipitate against known values

OXIDISING Aldehyde > Carboxylic acid [heat with acidified potassium dichromate (VI) ions (oxidising agent)] colour change: ORANGE to GREEN Ketone > Carboxylic acid X [acidified dichromate (VI) ions are not a strong enough oxidising agent] REDUCING: [LiAlH4 in dry ether] Aldehyde > Primary alcohol Carboxylic Acids They hydrogen bond with themselves as they do have a polar O-H+ bond. For this reason, carboxylic acids have very high boiling points. They can hydrogen bond with water due to their polar C+=O- bond. Oxygen uses its lone pair to form hydrogen bonds with H+ atoms on the water molecules. Therefore, carboxylic acids are soluble, however as they get bigger they become less soluble as the intermolecular forces get too strong. Dimer: 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. Ketone > Secondary alcohol

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 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) 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 WATER (produce carboxylic acid) - Vigorous reaction with cold water acyl chloride + H2O > COOH + HCl ALCOHOL (produce ester) - Violent reaction @298K acyl chloride + OH > COOCH + HCl AMMONIA (produce amide) - Violent reaction at 298K acyl chloride + NH3 > CONH2 + HCl AMINE (produce Nsub-amide) Violent reaction at 298K acyl chloride + CNH2 > CONH2C + 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

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

Forming a polyester Dicarboxylic acid + Diol > Polyester + Water

4.9 Spectroscopy and Chromatography

EM Radiation: Wavelength: Why: How: 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 O-H+ bonds. Cooking Microwave oven Surgery to kill cancer cells Chemical industry heating 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 a broken ethanol molecule. See below. 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 long Stationary phase is small particles of a solid coiled tube e.g. oil packed into a tube e.g. silica Tube is built into an oven Tube is not heated Sample injected and vaporised Sample forced through tube by high pressure Both rely on different amounts of the sample being moved from the top of the tube to the bottom known as the retention time ADV of HPLC over GC: HPLC can be used if sample is heat sensitive or has a high boiling point