why one molecu;e has more positive value for entropy?

Is ur value u got for

system entropy correct/ comment on the value u got?
Negative as expected bc

Gases have much higher entropies than solids as there are many more ways of arranging the entities than
solids or liquids / less ordered / more random(ness)

ZnCO3 (solid) has more atoms/electrons /is more complex/bigger than ZnO (solid)
Bc 1 mol on left side become 3 moles on right side//yes, as 9 molecules of gas are being changed to 10
molecules of gas (

Calculate Stotal, and explain the significance of the sign for this value.
If pos then spontaneous viceversa
for entropy and enthalpy use sign and units OR
enthalpy will be given or calculate from hess or born haber cycle

always convert kJ to joules

feasable means spontaneous

a reaction is spontaneous if gibbs free energy is negative or if total entropy is positive or if
activation energy is low

Calculate the minimum temperature, in kelvin, at which the reaction is spontaneous

always give answer in kelvin

formula is

0=system entropy - (reaction enthalpy)/T

Would u expect system entropy to be + ?

Yes bc 1 mol goes to 4 moles/particles (so more disorder) /increase in number of moles/particles (1)
products include a gas (and so more disorder) (1)

H is therefore negative and so Ssurroundings must be positive bc Surroundings gain energy so

more ways of arranging energy

Our calculated total entropy change is at 298K

If total entropy change is negative then natural direction of rxn is toward
the side of the reaction with lower entropy (COMMENT ON EQUIB
POSITION AT 298K)

Explain fully why a catalyst increases the rate of a reaction

A catalyst provides an alternative route with a lower activation energy/ which requires less energy (1)
so more collisions / particles have energy greater than the activation energy (1)
Kp depends only on temperature NOT ON conc of any reactants or products

Temperature effect on rate of rxn

As the temperature increases the energy of the particles increases (more particles to the right hand side
of EA line in diagram) and so more (successful) collisions/particles have energy greater / equal or greater
than the activation energy.

Is the sign of Ssystem (negative) as expected? Give a reason for your answer.
yes as 3 molecules in reactants become 1 molecule in products OR yes as (2) gases a liquid
Hetrgenous catalyst is one that is Not in same phase as reactants.
Homogenous is opposite ^

Higher temp and pressure increases rate of rxn so the reaction to form the
products is faster
In equilibrium qns talk about temp and pressure in terms of yield of products and
rate of rxn
Increasing pressure favours side with less molecules
If the forward rxn is exo increasing temp will shift equilibrium to left

In equilibrium constant expressions always write the state (g s l or aq) in brackets

Unit for Kp is atm^-2

Shaded area in activation energy / temperature graph shows fraction of molecules with energy EA

When catalyst is added to reaction the new activation energy line will be to the left of the orginal line as more molecules have energy great
than activation energy

How to measure rate/progress of rxn if gas is produced? (Describe, with the aid of a diagram, an
experiment)

Measure the volume of gas given off in a given time / count bubbles / obscuring cross using limewater (1)
and then repeat over a range of temperatures (1) plot graph (volume against temp) and cacl gradient
Positive enthalpy is endo

Neg enthalpy is exo

For endo rxn how do u increase product yieldf

Increase temperature / reduce pressure (1) Decreases Ssurroundings (negative) and hence increases
Stotal and le chatlier principles explained

Why does the value for Kp have no units?

) Same number of moles on each side of the equation OR The (partial pressure) units all cancel out (in
the expression for Kp)

Ways (properties) to measure progress or rate of rxn- color change colorimetry, volume of gas
produced,pressure, quenching titration (

as
OR ANOTHER WAY OF MEASURING VOLUME:

Put reactants on top pan balance and measure mass at time intervals but problem is mass changes are
small so v sensitive balances required

(iodine and h2o2)

Include only gasses in the Kp eqn

As Kp has such a small value, suggest THREE ways in which this industrial process could be
improved to increase profitability. Justify each of your suggestions

Increasing the pressure/ concentration of CO would force the reaction to the RHS with the smallest
number of gaseous molecules , Reduce the temperature so that the reaction goes in the exothermic
direction / increase the temperature to increase rate (1) Use a catalyst to increase rate / increase the
surface area of the nickel to increase number of collisions (1)

Ni(s) + 4CO(g) ->< Ni(CO)4(g)

The second stage of this process is to recover the nickel from the nickel tetracarbonyl, Ni(CO)4.
By considering your calculations of the entropy changes, suggest how this could be done. Justify
your suggestion.
The reaction can be reversed by increasing the temperature (1) as S surroundings will become
less positive/more negative as the temperature is increased (and Ssystem will remain a

Apart from heating the mixture, suggest what might be done to encourage the reaction to take
place. Explain why your suggestion is likely to work.

Dissolve solid(s) in water/solvent (before mixing) (1) Accept grind into a (fine) powder become mobile,
so increasing chance of collisions, (hence interactions) (1)

When these two solids are mixed together in a beaker, no reaction is observed. What
explanation can be given for this, in view of the fact that the process is spontaneous? )

Activation energy must be high / reaction must be kinetically hindered/reaction doesnt have to be fast

Only for Kp u need to calc partial pressure not for Kc

xxx

N2O4(g) >< 2NO2(g)

The magnitude of Ssystem for the reaction is greater than the magnitude of Ssurroundings.
Explain why this must be the case.
Stotal is positive as reaction occurs (1) So Ssystem must be more positive than Ssurroundings is
negative (1)

The reaction was repeated at the original pressure, but the temperature was increased to 75 C.
The value of Kc was approximately twenty times greater. How does this information show that
the reaction is endothermic?

As Kc is bigger, more NO2 is produced so heat helps forward reaction / by Le Chateliers principle
reaction goes forward to use up heat / as temperature increases Stotal must be more positive so
Ssurroundings (= H/T must be less negative

Xxx

IF PP OF ALL GASSES IN MIXTURE IS DOUBLED THEN KP HAS NO EFFECT

XXX

What does your answer to (iv) tell you about the extent of the reaction at 1123 K? Justify your answer

All products/reaction goes to completion because Stot > 200 J mol1 K1 OR bc Stot is very large

-x-

What does your answer to (ii) tell you about the position of the equilibrium?

Equilibrium lies to RHS/products side as Kp is large

Xxx

2NO(g) + O2(g) 2NO2(g)

If the total pressure of the reaction mixture was increased, describe what would happen to the value of
the equilibrium constant, Kp, and the partial pressure of NO2(g). In each case justify your answer.

Kp remains unchanged as pressure does not affect it / only temperature affects Kp

partial pressure of NO2 increases(mole fraction increases) as eqm moves to side of fewest (gas)
molecules/RHS

acids taste sour

naoh strong base

Pressure of gas I s caused by freq and momentum of collisions of gas molecules with container walls

Partial pres unit is atm

Conc of catalyst doesnt inc rate of exn
bond enthalpies differ in: so enthalpy change wont equal exactly 0

Extra cost of (building) equipment (to withstand higher pressure)

Ammonia / barium chloride is poisonous

assumptions for weak acid calc

Hydroxides get more soluble as you descend Group 2 (

S total gets less negative / more positive as you go from Ca(OH)2 to Ba(OH)2

Bromine colorimetretr

Increase atom economy:

Remove methanol/the product (as it is formed) (1) Recycle/reuse unreacted reactants

Caralyst: It provides an alternative (reaction) route/mechanism/gases adsorbed on catalyst surface

Calculate the minimum temperature needed for this reaction to be thermodynamically feasible.

Make s total = 0 and s surr= opp sign of actual s total value

Enthalpy divided by entropy of surr

xxx

ures. (i) The yield of ammonia produced at equilibrium is less at 700 K than at 298 K, if the pressure
remains constant. In terms of entropy, explain why this happens.

Higher T makes Ssurroundings decrease (so Stotal is less positive)

At dyn equib The concentrations of the products and reactants are not eq

Other than experimental error we can get anololy reslts on graph due to Active sites/surface (area) on
catalyst full/blocked/saturated (1) Because the reaction is at a higher concentration (of A)/ decreases
rate of reaction

Iodinde propane rxn add sodium thio to stop rxn by neutralizing the acid

Indicator is starch

H20 in exces for hydration rxn

Xxx

In sodiu ethanoate The ethanoate ions react with water to give hydroxide ions. So its slgjtly alkaline

A solution of a weak acid cannot be titrated with a weak base using an indicator to find the end-point
because A the pH change is too gradual close to the equivalence point.

Put only gasses in Kp eqn

Aim of industries is max yield at lowest cost

Suggest a reason why pressures greater than 300 atmospheres are not routinely used. Even if they
increzse yield

) Cost (of energy) to provide compression/ cost of equipment to withstand high P/ maintenance costs

Xxx

Suggest why this reaction takes place quickly at room temperature and pressure

The activation energy must be low

Xxx

Explain the meaning of spontaneous in a thermodynamic context.

S o total is positive
In which eqn does it act like a base in the eqn where lhs has less h ions than rhs bc base accepts h ions

phenolphthalein, which is colourless in acidic solutions, turn pink in alkaline solutions bc It forms a pink
anion by loss of H+ ions.

Citric acid oranges

Acid reacts w metal to produce hydrogen

Water can behave like acids and bases(amphoteric) it behaves like an acid with ammonia and as a base
with hydrochloric acid by donating and accepting protons respectively

H20 is liquid

All acids and bases are aq solutions

Ethanioic acid is a weak acid while hcl is a strng acid

-x-

Ed

Catalysts are used in exo rxns so faster rxn at a lower temp this produces more yield compared to
increased temp without catalyst (which can also be expensive)
Temp is the only factor that affects equib constant
In dynamic The equilibrium can be approached from either direction.

the time required for any specified property (e.g. the concentration of a substance in the body)
to decrease by half.
Anything in square brackets in conc
If gas and solid react rate of rxn is independent of pressure

Increase in temp causes rate to inc by a factor of

Mark x exermiment and note time taken for x to disappear

x-x

so exp and accurate ph meter reuired

If substance is not there in rate eqn then change in conc if that substance wont affect rate of rxn

Strong acids hcl and sulfuric

When calculations of ph of weak acid : we assumes that degree of ionisation of the acid is very
small/negligible

The graph of [I2] against time is a straight line, showing that the order of reaction with respect to iodine
is zero. (i) Explain why the propanone and the hydrogen ions must be in large excess in this experiment
in order to give this straight line.

(ensures that) [H+ ] and [propanone] (virtually) constant bc only the [I2] changes

What further experiment could be done to show that the order of reaction with respect to propanone is
one? State the effect of this change on the graph.

double the concentration of propanone and slope or gradient changes/increases/decreases by same

factor

Stotal is positive because Ssurr is (numerically) greater than Ssys

ammonia is a weak base
In the case of hydrochloric acid, dilution by a factor of 10 increases the pH by one unit. Suggest why
ethanoic acid behaves differently.

(Dilution/addition of water) shifts the equilibrium to the right so the decrease in [H+ ] is less than
expected
Ph of weak base same steps as ph for weak acids except one additional step

In ka expressions you need concentrations so find ways to convert to concentrations numerators values
will be same

Stronger acids should calc the equib conc from ice table not like weak acids where u can just take incital
conc=equib from eqn

Ph for strong bases

When solving qns first identify if its a strong/weak acid/base
Iodine and propanone react in the presence of an aqueous acid catalyst as follows CH3COCH3 + I2
CH3COCH2I + HI
Sodium hydrogencarbonate stops the reaction by neutralizing the acid catalyst.

ALWAYS kp calculations in atm

Because Stotal increases equilibrium constant increases
what evidenvce two steps The number(s) (of particles) in the rate equation / rate-determining step do
not match those in the equation for the reaction

Weak acid ka assumption no H+ from the (ionization of) water

If no oh in products cant use titration

10 times dilution increases ph by 1

Explain, in terms of your answers to (a) and (b)(i), why an increase in the pressure leads to a decrease in
yield in reaction I.

mole fractions/partial pressures of numerator decrease // to maintain Kp constant, mole fractions of

numerator must decrease OR mole fractions of denominator must increase as PT 2 overall) // PT 4 /PT
) Increasing the pressure on this heterogeneously-catalysed reaction I has very little effect on the rate of
the reaction. Suggest why this is so. Reaction takes place on surface of the catalyst (1) Active
sites/(catalyst) surface is saturated with reactant molecules/reactants (at the pressure of the reaction)

Although industrial processes are often discussed in terms of equilibria, they are rarely allowed to reach
equilibrium. Not a closed system converted to kelvin

Stotal is positive because Ssurr is (numerically) greater than Ssys

(measure the) time taken (for the blue-black colour to appear) and temperature t

I2 not involved in rate-determining step/ so there must be another step where I2 is involved/

Neucleophilic substitutions :
Sn1 =k(halogenoalkane)

Tertiary:

) Explain why primary and tertiary bromoalkanes are hydrolysed by different mechanisms(Primary and
tertiary) carbocation intermediates have different stabilities (1) as (inductive effects of) alkyl groups
stabilise tertiary carbocation (1)

Entropy of element

exothermic as yield / pp of ethanoic acid / conversion of reactants/ Kp is higher at lower temperature /

as equilibrium moves (right) at lower temperature

catalyst adv Reaction can occur at lower temperature / has lower activation energy / requires less
energy (1) less fuel needed

pH = 4.8 / 4.77 (1) pH = pKa / [H+ ] = Ka (when acid is half neutralized) (1)

Both [H+]and [OH- ] have increased by the same amountSuitable reaction vessel e.g. side arm conical
flask / flask with delivery tubing attached via bung /