1.

(a)

(i)

2Ca(NO3)2 2CaO + 4NO2 + O2 formulae correct (1) balance (1). Ignore any state symbols. The balance mark is not stan !alone. 2

(ii)

steam " fi##ing soun " crumbles (1) soli s$ells u% " milky li&ui %ro uce " comment about s%aringly soluble substance (1) CaO + '2O Ca(O')2 (1) ignore any state symbols 3 (

(iii) (i))

less (1) (Cat)ion si#e increases o$n the *rou% " charge ensity ecreases (1) (not atom si#e) The %olari#ing %o$er of the cation ecreases o$n the *rou% (1).

The less %olari#e the anion is by the cation the more ifficult the nitrate is to ecom%ose (1). +olarisation mark coul come from ,the less the electron clou is istorte -. or tren in cation si#e (1) com%arison of the lattice energies of the nitrate an the o/i e (1) balance in fa)our of o/i e at to% of grou% an the nitrate at the bottom (1) 3 (b) (i) (ii) same number of %articles in a smaller )olume " gas ensity increase (1) (

comment relate to the number of molecules on each si e to e/%lain a shift to l.h.s. (1) (not 0ust , ue to 1e Chatelier-.) so at higher %ressure e&uilibrium mo)es to fa)our N 2O4 (1) 2 K% 2 p(NO2)2 p(N2O4) There must be some symbolism for %ressure3 an no 4 5 ( (K% 2 p(NO2)2 2 46) p(N2O4) p(NO2)2 2 46 7 8.(9 2 :.2 (1) p(NO2) 2 2.: (1) atm (1) acce%t 2.;63 " 2.;6 " 2.: <ns$er an units con itional on (iii). 3
[16]

(iii)

(i))

2.

(a)

(i)

'Cl= %' 2 (.(3 4'+5 2 8.8:4 mol m!3 4'Cl5 2 8.8:4 mol m!3 48.8:4 to 8.8:4(35 'OCl= %' 2 4.23 4'+5 2 9.6> 7 (8!9 mol m!3 (1) ?a 2 4'+5 4OCl!5 (1) 4'OCl5 4'+5 2 4OCl!5 (1) or im%lie later in calculation 4'OCl5 2 4'+52" ?a 2 8.8>32 mol m!3 (1) 4'+5 2 8.(8 " 8.(84: " 8.(89 (1) '2@O4 '+ + '@O4!(1)
+

(ii)

(b)

(i) (ii)

or
!

'2@O4 + '2O '3 O + '@O4 ignore state symbols '@O4! '+ + @O42! (1) Aust be '3O+ + @O42! ignore state symbols 4

'2@O4 + '2O (iii)

secon ionisation su%%resse by the first ionisation (1)

?c =
(c) (i) (ii) 4'Cl

4Cl 2 5 2 4' 2 O5 2 4'Cl54 4O 2 5

+ O2 2Cl2 + 2'2O 8.898 (1) 8.38 an 8.38 (1) 8.8898 8.838 8.838 (mol!( m3) (1) (

e&uilibrium mols 8.28 4 5 e& B (8 (1) 8.828 48.82854 / 48.8895 ( ) (i) (ii) (iii)

?c 2 48.83852 / 48.83852 2 (8(8 or (8(2 or (8(3 or (8(2.9 4

<s reaction (left to right) is e/othermic (1) Cecrease in tem%erature ri)es e&uilibrium to from left to right (1)

2 2

<s more (gas) molecules on the left (1)3 e&uilibrium is ri)en from left to right (1) < catalyst has no effect (1) <s it only alters the rate of the reaction not the %osition of e&uilibrium " it alters the rate of the for$ar an re)erse reactions e&ually (1) 2
[20]

3.

(a)

@till reacting " rate of for$ar reaction an back$ar reaction e&ual " im%lication that for$ar an back$ar reactions are still taking %lace (1) Dut concentrations constant " no macrosco%ic changes (1) 2 Temp Press (Increases) Increases"faster (1) 1eft " to @O2 " to en othermic " lo$er yiel (1) Eight to @O3 " to smaller number of molecules (1) 3

(b)

(c)

(i)

Increases rate " or suitable comment on rate (1) Ao)es %osition of e&uilibrium to en othermic si e " or suitable comment on e&uilibrium such as reasonable yiel " less @O3 (1) Either com%romise in $hich the rate is more im%ortant than the %osition of e&uilibrium or o%timum tem%erature for catalyst to o%erate or )ali economic argument (1) 3

(ii)

Increases rate " more @O3 " only nee s small %ressure to ensure gas %asses through %lant " high or reasonable yiel obtaine at ( atms or at lo$ %ressure any$ay (1) and references to economic cost against yiel benefit e.g increase in %ressure $oul increase yiel of %ro uct but the increase in yiel $oul not offset the cost of increasing the %ressure (1) 2

(iii) ( ) (e)

Catalyst s%ee s u% reaction (1)

( (

Fana ium (F) o/i e " )ana ium %ento/i e " F2O9 (1)

<ny one use production of fertili#ers3 etergents3 yes3 %aints3 %harmaceuticals (in) car batteries3 %ickling metal (
[13]

+@O2 2 +O2 4. (a) (i) K% 2 +@O3 2 (1) ( [ ] no mark ( ) OK

(ii) Aols at start mols at e&u

2@O3 2 8.9

2@O2 8 (.9

+ O2 8 8.:9 (1)

Mark by process ( mark for $orking out mole fraction ( mark for 7 (8 ( mark for correct substitution in ?% an ans$er ( mark for unit

i.e.

(.9 +@O2 2 2.:9 7 (8 2 9.4; 8.: 2 +O2 2 .:9 7 (8 2 2.:3 8.9 +@O32 2.:9 7 (8 2 (.63

n.b. could show mole fraction for all 3 and then 10 later to i!e partial pressure. ?% 2 (9.4;)2 7 (2.:3) " ((.63)2 2 24.9 (1) atm (1) (b) (i) (ii) No effect (1) No effect (1) 9 ( (
[8]

5.

(a)

(i)

fraction of the total %ressure generate by a gas or or %ressure gas $oul generate if it alone occu%ie the )olume or +total 7 mol fraction (1) %(CO) %(' 2 ) 3 %(C' 4 ) %(' 2 O) (1)

(ii) (iii)

?% =

not 4 5

Increase in total %ressure $ill result in less %ro uct molecules in the e&uilibrium mi/ture " e&uilibrium mo)es to left (1) because more molecules on %ro uct si e of the e&uilibrium than on left (1) No change (1)

2 (

(b)

(i)

(ii)

?+ increase (1) No change (1)

(iii)

(c)

(i)

?% =

( %(C' 4 ) (1)
; (

(ii)

>.6: 7 (8!3 k+a!(" >.6: 7 (8 "llow 3 # $ si fi

+a

conse&uential on (i) (1)

(iii)

e&uilibrium has mo)e left in fa)our of gas (1) e/othermic going left to right"in the for$ar irection " as $ritten (1) %tand alone <ns$er yes or no $ith some sensible 0ustification (1) e.g. No the costs $oul not 0ustify the amount %ro uce

(i))

(
[12]

6.

(a)

(i)

?c 2 4@O352 " 4@O252 4O25 (1)

(ii)

8.2 38
2 3.33 (8
3

8.( ;8

(. 6 ;8

(.;: (8!3 8.83 (1) 2 (8.83) 3 2 3 ?c 2 (3.33 (8 ) (.;: (8 2 46;8or 4.6; (8 4 (1) mol (b) (i)
(

m3 (1)

3 (

?c ecreases (1) shifts to left " in re)erse (1) no effect (1) no effect (1) ?% 2 %@O32 " %@O22 %O2 (1) %enalise s&uare brackets

(ii) (c) (i) (ii)

( ( (

( )

(i)

(ii)

Total number of moles (1) conse&uential on a (ii) @O2 2 8.8>92(4)G O2 2 8.84:; (2)G @O3 2 8.69: (() (1) +artial %ressures= @O2 2 8. (>8 (9) atmG O2 2 8.8>92 (4) atmG @O3 2 (.:((4) atm (1) i.e. multi%ly ans$er in (ii) by 2 (.:(42 " 8.(>892 8.8>924 2 698 (1) atm
(

(iii)

(i))

(1)

2
[14]

(a)

+ressure e/erte by the gas if it alone occu%ie the same )olume at the same tem%erature"mole fraction 7 total %ressure

p ( N 2 ) p (O 2 )
(b) (i) (ii) K% 2

p ( NO) 2

Correct number of moles (1) Correct mole fractions (1) Correct %artial %ressures (1) 2.49 7 (83 (1) "''()* +#, %-

(c)

K% increases (1) H&uilibrium mo)es to r.h.s. (1) $hich is the e/othermic irection (1) 3 ( 2
[12]

( )

(i) (ii)

K% . p (Ni(CO)4) " p(CO)4 'igh %artial %ressure with some reason (1) so the %ressure Ni(CO)4 increases to kee% ?% constant. (1)

!.

(a)

(i) (ii)

K+ 2 % (CO2) (.46 (atm)

allow without brackets/ 012O3( % 4 5

)enalise wron unit

( "nswer is conse&uential on (a) (i) e. . (.46 must ha!e atm!(

%(Cl 2 ) %(NO) 2

(b)

(i) (ii)

K% 2

(%(NOCl)) 2

allow without brackets/ penalise 4 5 2NO + Cl2 8 +8.(( 8.(( 8.8>>(8 8.4>9

2NOCl

@tart ( 8 !8.22 +8.22 e& moles 8.:6 8.22 total moles of gas (.(( mole fractions abo)e )alues B(.(( (1) 8.:82: 8.(>62 %artial %ressure " atm abo)e )alues 7 9.88 (1) 3.9( 8.>>( 2 8.4>9 atm (8.>>( atm) (3.9( atm) 2 K 2 (1)
%

(1)

2 8.83>9" 8.83>4 atm (1) ran e of answers 0.0,04 5 0.0,1 0.036 5 0.036+ 2O* 0.0, "''()* + %. 'orrect answer plus some reco nisable workin (5) 7arks are for processes

(&uilibrium moles 8i!idin b9 total moles 7ultipl9in b9 total pressure %ubstitutin equilibrium !alues into e:pression for K)
'alculatin the !alue of K+ with correct conse&uential unit. (iii) <s the reaction is en othermic ! stand alone (1) the )alue of K+ $ill increase (as the tem%erature is increase ) I (1) conse&uential on 1st answer (if e:othermic (") then K+ decreases (1)) -or effect on K+ mark/ must ha!e addressed whether reaction is endothermic or e:othermic (i)) #ecause (as the )alue of K+ goes u%)3 the )alue of %Cl2 7 (%NO)2 " (%NOCl)2 (the &uotient) must a$so go u% (1) an so the %osition of e&uilibrium mo)es to the right ! stand alone (1) But mark conse&uentiall9 on chan e in ? in (iii) 0f ;position of e&uilibrium mo!es to ri ht so ?p increases< (ma% 1) 012O3( references to =e 'hatelier>s )rinciple
[12]

&.

(a)

Hnthal%y"heat"energy change for one mo$e of a com%oun "substance" a %ro uct (1) '(T soli "molecule"s%ecies"element 3e?ect ;heat released or heat re&uired< unless both mentioned to be forme from its e$ements in their standard states (1) <11OJ normal %hysical state if linke to stan ar con itions 3e?ect ;natural state< 5 ;most stable state< stan ar con itions of ( atm %ressure an a state tem%erature (2>6 ?) (1) 3e?ect ;room temperature and pressure< 3e?ect ;under standard conditions< 3

(b)

(i)

Don s broken NKN (+)>49 an ( + )(386

Don s ma e ;N!' (!)234; (1)

3'!' ( + ) 2293 (1) L' 2 >49 +(386 ! 234; 2 !>3 sign an )alue (1) L@M 2 !>3 2 !4;.9 (kN mol!() sign an )alue & on 3r mark (1) 2 "ccept #,A.$ (kB mol#1) with workin (4) "ccept C ,A.$ with workin max (3) "ccept C63 with workin ma: (2) (ii) N
2

+ (3 )'

(H n th a l% y )

@ OE !>3 (2 )N '
3

"ccept #,A.$ Correct labelle le)els (1) 3e?ect ;3eactants< and ;)roducts< as labels L' labelle (1) irection of arro$ must agree $ith thermicity "ccept double headed arrow 8ia ram marks c& on si n and !alue of D@ in (b)(i) 012O3( acti!ation ener 9 humps (iii) 398!988 OC (1) "ccept an9 temperature or ran e within this ran e
8

higher tem%erature gi)es higher rate (1) but a lo$er yiel because reaction is e/othermic (1) "ccept fa!ours endothermic reaction more than e:othermic so lower 9ield OE 1o$er tem%erature gi)e higher yiel because reaction is e/othermic (1) but rate is slo$er (1) "ccept c& on si n of D@f in (b)(i) or le!els in (ii) 3e?ect lower temp fa!ours e:othermic reaction (i)) Iron " Pe (1) I*NOEH any %romoters no effect on yiel (1) tem% $oul ha)e to be much higher for a reasonable rate then yiel $oul be too lo$ Qlo$er acti)ation energyR im%lies reasonable rate OE <llo$s reaction at a lo$er tem% at a reasonable"fast rate gi)ing a reasonable yiel . "ccept rate too slow without catal9st at a temp i!in a reasonable 9ield 3e?ect to lower acti!ation ener 9 of reaction (c) (i) a )antage higher (e&uilibrium) yiel "more N'3 in e&uilibrium mi/ture"e&uilibrium shifts to right (1) because smaller number of (gaseous) moles"molecules on rhs (1) 012O3( an9 reference to chan e in rate 3e?ect ?ust ;more ammonia< 2

())

(ii)

isa )antage (%lant more) e/%ensi)e because thicker %i%es $oul be nee e O3 cost (of energy) for com%ressing the gases"cost of %um% OE Cost of e&ui%ment"%ressure not 0ustifie by higher yiel "ccept stron er or withstand hi h pressure for thicker "ccept !essel5container5plant 5e&uipment5reaction !essels for pipes 3e?ect ;?ust more e:pensi!e< 3e?ect ;?ust thicker pipes etc< 3e?ect apparatus
[18]

1".

(a)

)*'(+E s.,. throu-hout this .uestion (i) mo$es /(2 ((8.8 ! >.88) 2 (.88 (mol) mo$es (2 (9.88 ! 4.98) 2 8.988 (mol) mo$es /(3 >.88 (mol) all 3 correct S (2) 2 correct S (1) 3e?ect multiples of the stated moles (ii) <ll three B total number of moles (1) i.e. 2

(.88 (= 8.8>92) or 2 2( (8.9 8.988 E O2 = (= 8.84:;) or ( 2( (8.9 >.88 E %O3 = ( 8.69:) or (6 2( or ; : (8.9 E %O2 =
3e?ect roundin to 1 si fi 7ark conse&uential on (a)(i) (

10

(iii)

<ll three 7 total %ressure (1) i.e.

(.88 2.88 or 4 2( %@O2 2 (8.9

2 8.(>8 (atm) 8.988 2.88 or 2 2( (8 . 9 2

%O2

2 8.8>92 (atm) >.88 2.88 or 3; 2( or (2 : (8 . 9 %@O3 2 2 (.:( (atm) 7ark conse&uential on (a)(ii) (

Kp =
(i))

((.:() 2 (8.(>8) 2 (8.8>92)

Kp 2 69( (1) atm!( (1) 7ark conse&uential on (a)(iii) and (a)(i!) "ccept answer with units and no workin (+) "ccept ;correct answers< between 4,$ and 4$$ as this co!ers roundin up etc 3e?ect wron units e. . mol#1 dm3 (b) (i) (K%) ecreases (K% ecreases so) 3e?ect an9 =e 'hatelier ar ument (this pre!ents access to 1 st mark) ( 2

(ii)

p 2 %O3
2 fraction"&uotient p %O2 pO 2 has to ecrease (to e&ual ne$ k%) (1)

so shifts to $e,t han si e (1) 0 this mark only a)ailable if (b)(i) ans$er $as k% ecreases. 3e?ect shifts to ri ht/ even if answer to (b)(i) was kp increases (as (c) (i) % @O 3 ecreases $hereas % @O 2 an % O2 increase) 2 (

No effect"none"#ero (effect)

11

(ii)

Increases O3 more @O3"more sul%hur trio/i e O3 increases amount of @O3"sul%hur trio/i e (

( )

(i) (ii)

No effect"none"#ero (effect) No effect"none"#ero (effect)

( (
[13]

11.

(a)

O ' C O ' C ' ' C ' '

( ( Aoles= C2'9O'= 3.:9 (1) Aoles= 'COOC2'9 = 2.98 an moles '2O = 2.98 (1) ,or both 4 'COOC 2 ' 9 54' 2 O5 4'COO'54C 2 ' 9 O'5 3e?ect ob!iousl9 round brackets ( ) 2

(b) (c)

ester (i)

(ii)

Kc =

12

2.98 Kc =

8.469

2.98 3.:9

8.469

(iii)

8.469 8.469 (1) Aust ha)e clearly i)i e moles of each com%onent by 8.469 for (st mark e.g. 4'COOC2'95 2 4'2O5 2 9.(; (mol m!3)

8.98

an 4'COO'5 2 (.83 (mol m!3) an 4C2'9O'5 2 :.:3 (mol m!3) 2 3.33 (1) stand a$one mark I*NOEH sig.figs.
(+.$0) + 0.$0 3.F$ . 3.33 onl9 scores (2) if it is stated "ccept that G cancels either here or in (i!) Kc =

0f [@+O] omitted in (ii)/ then answer Kc . 0.A,F mol#1 dm3 (2) but this will i!e Kc . 1.33 mol#1 dm3 with G omitted from calculation (1) 3e?ect 1st mark if ,4$ used as G in e:pression (i)) No3 (as) e&ual numbers of moles on both si es OE )olumes cancel OE mol m!3 cancel OE units cancel OE crossing out units to sho$ they cancel "ccept ;e&ual powers5moles on both sides< O3 ;powers cancel< 7ark 'H on Kc e:pression in (ii) 3e?ect concentrations cancel ( ) (i) (as reaction) en othermic (1) "ccept e:othermic in backward direction (or words to that effect) ?c ecreases (1) 0f state e:othermic in forward direction/ 1 mark only (out of 4) for 'H ;increase in Kc< numerator in &uotient (has to) ecrease OE enominator in &uotient (has to) increase OE fraction (has to) ecrease (1) yiel of 'COOC2'9 ecreases (1) 4

13

(ii)

no effect as catalysts o not affect (the )alue of) ? OE no effect as catalysts o not affect the %osition of e&uilibrium OE no effect as catalysts o not affect the yiel OE No effect as catalysts increase the rate of the for$ar an back$ar reactions e&ually"to the same e/tent OE no effect as catalysts on$y increase the rate OE no effect as catalysts on$y alter the rate Qno effectR can be state or im%lie I*NOEH any references to acti)ation energy 3e?ect ?ust ;catal9sts increase rate<
[13]

12.

(a)

The amount of a so$id %resent is immaterial since Kc oes not e%en on this OE so$ids o not a%%ear in e/%ression for e&uilibrium constants I*NOEH any references to soli in e/cess. <g+ + I! <gI I*NOEH state symbols (

(b)

14

(c)

Correct ans$er $ith some $orking an correct units scores full marks. Other$ise ste%s in calculation must make it reasonably clear to e/aminer $hat is being calculate (TJC). (initial amount) I! 2 8.(88 mol m!3 7 8.898 m3 2 9 7 (8!3 mol (1) <mount <g+ 2 8.(88 mol m!3 7 8.83( m3 2 3.( 7 (8!3 mol (1) e&uilibrium amount I! 2 3.( 7 (8!3 mol (1) I! reacte 2 (9 ! 3.() 7 (8!3 mol 2 (.> 7 (8!3 mol (1) If this subtraction is not carrie out then the ne/t mark (for calculating amount of sul%hate) can not be a$ar e . Thus amount of sul%hate 2 U 7 (.> 7 (8!3 (2 >.9 7 (8!4 mol) (1)

3.( (8 3 mol
conc io i e 2

8.89 m 3

(2 8.8;2 mol m!3) 8.>9 (8 3 mol

8.89 m 3 <NC conc sul%hate 2 (2 8.8(> mol m!3) (1) The mark is for the %rocess of i)i ing by 8.89 m3
Kc 2 8.8(>"8.8;22 2 4.>4 (1) <ns$er must be to 2 or more @.P. Falue conse&uential on i)i ing their moles by a )olume. mol!( m3 (1) @tan alone 6
[10]

13.

(a)

(i)

+airs= aci N'4+ "ammonium ion an base N'3 "ammonia aci '3O+ " hy ronium ion an base '2O " $ater "ccept h9dro:onium ion 4 N' 3 54' 3 O + 5 (

(ii)

Ka 2

4 N' 4 5

ignore lo$er case k [2@ 3 ][@ + ]

"ccept Ka .

[2@ , ]

3e?ect answers includin [@+O]

15

(iii)

4'3O+5 2 (8!9 mol m!3 (1) <ssum%tion ioni#ation of N'4+ (negligibly) small (1) <ssum%tion 4N'35 2 4'3O+5 (1) "ccept [2@,C] . [2@,'l] or 2@,'l totall9 ioniIed thus 4N'4Cl5 2 (( 7 (8!9)2 " 9.;2 7 (8!(8 2 8.(:6 mol m!3 (1) <ns$er to 2 or more @.P. 4

(i))

TJC methyl re (1) in icator constant or %KIn must be near the en %oint %' OE in icator constant or %KIn must be near 9 (1) 2n mark con itional on correct in icator "ccept pK0n in the steep part of the raph or it is a weak baseJ stron acid titration 2

(b)

CN! + '2O

'CN + O'! ( ; ( "ccept ;K< instead of ;

I*NOEH state symbols

(c)

(i)

nucleo%hilic a

ition

16

(ii) O (=) C O C C N

(=)C N (1) ,or both arro1s

(1 )

(1) ,or intermediate

O (=) C CN

'

CN

O ' C CN
+

(=)C N

OE for secon ste% O (=) C C N (1 ) -ish hook arrows (penalise once) V Ignore the grou%s attache to the carbonyl carbon throughout V The interme iate is not conse&uential on their first ste% V The minus of the cyani e ion can be on either the C or the N V The arro$ can start from the minus of !CN in ste% ( (but not from the minus of CN!) an can start from the minus of O! in ste% 2 V The arro$ from the bon must not go %ast the O atom V 1one %airs not essential V @ingle ste% a ition of 'CN or initial attack by ' +"'CN scores #ero ' O ' C C N 3

V <utoionisation of C2O can only score the last t$o marks ie ma/ 2 (iii) TJC if too aci ic too small a concentration of cyani e ions (1) "ccept not enou h 5 too little '2# if too alkaline too little 'CN to onate the %roton in the last ste% OE '+ ion concentration too lo$ (1) 2

17

( )

(i)

rate 2 k4C'3C'2C'2Cl5 4CN!5 Aust be an e&uation Aust be 4 5 NOT ( ) Ignore u%%er case ? "ccept L3> or Lr> for rate '3@F'l] 5 [1Jchloropropane]5 [chloropropane] "ccept [c9anide ion]5[c9anide] 3e?ect [K'2] (

(ii) ' ' ! N C C C 2' Cl

9

! ' N C C C 2' ' C l

9

' N C C C 2' ' + C l

9

C u rly a rro $ C u rly a rro $ (1 )

(1 ) T ra n s itio n s ta te (1 )

V Aust ha)e %artial bon s in transition state V CN an Cl must be on o%%osite si es of central C in the transition state V <cce%t negati)e charge on N of cyani e ion 7echanism based on %21 scores 0 3e?ect fish hook arrows (penalise once) 3e?ect arrow from 2 of '2
[19]

14.

(a)

N"N2 goes from 8 to !3 2 re uction (1) '"'2 goes from 8 to (+)( 2 o/i ation (1) 0f ;the o:idation number of 2 oes down hence reduced and the o:idation number of @ oes up and hence o:idised< (max 1) 0f all O.2. correct but fails to state which is o:idation and which is reduction scores 1. 0f all O.2. correct but both reactions misclassified/ scores Iero. "n9 answer not referrin to nitro en or h9dro en scores Iero. 2

18

(b)

(i)

Calculation of bon s broken 4;3 7 3 + >44" (2 2292) (1) Calculation of bon s ma e 3667;" (2 2326) (1) L@ 2 !:; (kN mol!() (1) mark conse&uential on numerical )alues calculate abo)e 'orrect answer with some workin scores 3 marks 'orrect answer alone scores + marks

(ii)

<)erage " mean bon enthal%y use for '02 bond 3 ammonia 3e?ect ?ust ;a!era e bond enthalpies used<

(iii)

Thermo ynamic= energy le)el of %ro ucts lo$er than that of reactants OE energy release in bon formation W energy use to break bon s (1) "ccept D@ ne ati!e 5 reaction e:othermic kinetic= hi-h acti)ation energy (1) because strong NKN (1) 4confusion bet$een thermo ynamic an kinetic loses first 2 marks5. "ccept because 2M2 is 6,,5 total bond breakin ener 9 is hi h5++$+(kB mol#1) 3

19

(c)

(i)

TJC One $ay tem%erature increase therefore molecules ha)e greater (a)erage kinetic) energy (1) "ccept mo!in faster more molecules"collisions ha)e H X Hact (1) Therefore a greater proportion of" more o, the collisions are successful (1) Ignore greater fre&uency of collision "ccept ( N (act particles for molecules reater fre&uenc9 of successful collisions5 more successful conditions per unit time 3e?ect ?ust ;more successful collisions< <nother $ay a ition of (iron) catalyst (1) "ccept platinum catal9st 3e?ect incorrect catal9st %ro)i es alternati)e route of lo$er acti)ation energy (1) HIT'HE= < greater %ro%ortion of "more of the molecules"collisions ha)e H X H cat" a greater %ro%ortion of collisions are successful 3e?ect ?ust ;more successful collisions< OE %ro)i es (acti)e) sites ($here reactant molecules can bon " be a sorbe ) (1) Ignore any ans$ers referring to %ressure or concentration. Co not %enalise 0ust Qmore collisions are successfulR more than once

(ii)

456 Cecrease tem%erature (1) because (for$ar ) reaction e/othermic (1) increase %ressure (1) because more moles (of gas) on left (1) "ccept low temperature D@ is ne ati!e "nswer based on endothermic reaction scores 0 "ccept hi h pressure "ccept molecules for moles

[19]

20

15.

(a)

(i)

To slo$ o$n the reaction"to sto% the reaction OE to &uench the reaction OE to free#e the (%osition of) e&uilibrium OO**( (1) so that the (e&uilibrium) concentrations"amounts o not change (1) "ccept to stop e&uilibrium shiftin to the left 2

(ii)

7irst mark8
4 @ 2( ) 5 = 4 0 2 ( ) 5

OE Yse of (9.8 7 (8!4)2 (1) 0f [@0] not s&uared/ first mark onl9. /econd mark8
4 @0 ( ) 5 2 = (9.8 (8 4 ) 2 8.8(>

OE (9.8 (8 4 ) 2 8.8(> 2 OE 4 'I (g) 5 2

4'I(g)5 2

(9.8 (8 4 ) 2 8.8(>

(1)

Third mark8 4'I(g)5 2 3.; 7 (8!3 (mol m!3) (1) Correct ans$er scores 3 marks. Ignore state symbols. Ignore units unless $rong. Ignore s.f. 0f first mark not awarded/ total (0)
2 p @0 Kp = p @2 p 02

(b)

(i)

Ignore %osition of any ( ) [ ] !ore (0)

21

(ii)

(ach step of this calculation must be looked at. (st mark is for calculating e&uilibrium moles Z2 2 8.2 [2 2 8.2 Z[ 2 (.; (1) 7ark conse&uentiall9 2n mark is for i)i ing these by 2 (to get mole fractions) 8.2 :@ 2 = = 8.( 2.8 8.2 : 02 = = 8.( 2.8 (.; : @0 = = 8.6 2.8 (1) 7ark conse&uentiall9 3 mark is for multi%lying by (.( (to get %artial %ressures) 8.2 +@ 2 = (.( 2.8 2 8.(( (atm) 8.2 +0 2 = (( 2.8 2 8.(( (atm) (.; +@0 = (( 2.8 2 8.66 (atm) (1) 7ark conse&uentiall9 4th mark is for substituting into their e/%ression an calculating K%
(8.66) 2 (8.(() (8.(() 2 ;4 (1) Kp =
r

0 nore s.f. 'orrect answer with no workin scores (1) 0f moles @0 i!en as 0.4/ Kp . 1A ma: (3)

22

(iii)

@ame number of moles on each si e OE (Total) %ressure cancels OE (+ressure) units cancel (Aay be sho$n by crossing out etc. in b(ii)) "ccept L)owers cancel> O3 L*he9 cancel> O3 L%ame number of molecules on each side> 3e?ect L"artial pressures cancel> O3 Lmol dm#3 cancel>

[11]

?% = 16. (a) (i)

( p 2O ) 2 p 2 2 p O2 (

<llo$ ans$er $ith brackets an "or Q/R omitte Ignore (g) an e& ?% = "ccept p 2 2O p 2 2 p O2

3e?ect an9thin in [ ] (ii) @ame number of moles on each si e of the e&uation OE The (%artial %ressure) units all cancel out (in the e/%ression for ? %) (%NO)2 2 8.6: 7 8.23 7 9.8 7 (8!3( (1) 2 (.8 7 (8!3( %NO 2 \((.8 7 (8!3() 2 3.2 7 (8!(; (atm) (1) "ccept 3.1A 10#1A (atm) (1) Ignore sig fig Aark conse&uentially only if base on reci%rocal of correct e/%ression in (a)(i) 8.6: + 8.23 (+ 3.2 7 (8!(;) 2 (.(8 " (.( (atm) <llo$ TH from (b)(i) 3e?ect answer based on addin 2 # p2O ( 2

(b)

(i)

(ii)

23

(iii)

%NO oubles"$ill become ;.4 7 (8!(; atm (1) ?% remains constant"is (still) 9.8 7 (8!3( (1) Ignore any QneutralR &ualifications to these ans$ers "ccept p2O will increase 3e?ect more than double 3e?ect answers with incorrect reasonin 2

(c)

(i)

Eeaction $ill occur3 but ()ery) $itt$e NO is forme OE the e&uilibrium mi/ture is mainly (unreacte ) N2 an O2 "ccept reaction occurs/ but e&uilibrium lies (!er9 much) to the left 3e?ect ;3eaction is more likel9 to occur from ri ht to left< O3 ;3e!erse reaction is fa!oured</ unless included with acceptable answer

(ii)

No change of state of any of the com%onents is in)ol)e (as the gases are heate u%) OJTTH OE <ll com%onents are gases (at these tem%eratures) I*NOEH <ny reference to the number of %articles in)ol)e (

(iii)

(L@ is %ositi)e so)

' T 2 L@ surroun

ings

$ill be negati)e (

No mark for Qnegati)eR alone "ccept ne ati!e/ since for an endothermic reaction ener 9 is taken from the surroundin s causin a decrease in disorder 5 reduction in entrop9 (i)) (<s T increases) L@surroun becomes greater"less negati)e"

ings

more %ositi)e3 so L@total (also) becomes greater"less negati)e"more %ositi)e"increases "ccept D%surroundin s becomes ;smaller</ if &ualified/ e. . becomes closer to Iero (

24

( )

H&uilibrium might not ha)e been reache (in the )ery short time the gases are %resent in the engine) Ignore references to the fact that the system is not Qclose R "ccept other ases are present in the air (apart from 2+ and O+) "ccept temperature inside en ine ma9 be less than 1$00K "ccept actual (total) pressure ma9 be less than that assumed
[12]

Kp =
1 . (a)

2 p 2O 2

p 2 2 O4
( 3e?ect [ ] p 2O2

012O3( P20*% @(3(

(b)

(i)

2 8.6 7 (.( 2 8.66 (atm) and 2 8.2 7 (.( 2 8.22 (atm) (1) (8.66) 2 K 2 (8.22)
p

p 2 2O2

Kp 2 3.92 (1) atm (1) %('O28 7"3K 0% 'H O2 )"3*0"= )3(%%P3(% "% '"='P="*(8 3

25

(ii)

7irst mark8 E 2 2 O4 2 8.(8 E 2O2 2 8.>8 (1) 3e?ect Q /econd mark8 Kp constant or use of Kp 2 3.92 or use of Kp calculate in (b)(i) (1) Third mark8 Falue of +T $ith some $orking e.g.

( E 2O2 +T ) 2
3.92 2

E 2 2O4 +T

8.6( 3.92 2 8.(8 7 +T

+T 2 8.439 (atm) (1) 7ark 'H on first and second answers to (b)(ii) "ccept in ran e 0.,3 to 0.,, *@038 7"3K 2O* "G"0="Q=( 0- Kp (E)3(%%0O2 8O(% 2O* 'O2*"02 " p+ *(37 (c) (i) Increases " gets larger" gets bigger" goes u%"greater 3e?ect more 3 (

26

(ii)

7irst mark8
2 p 2O 2

p Praction"&uotient" 2 2O4 "numerator has to increase (to e&ual ne$ Kp) (1)
/econd mark (can on$y be a1arded ,or an ans1er that re,ers to the ,raction3.uotient abo9e)8 E)T2E+ p p 2 2 O4 so shifts to +)*2T han si e (as 2O2 ] an ^) " p p 2 2O4 goes in for$ar irection (as 2O2 ] an ^) (+ so (more) N2O4 changes to NO2 (+ so (e&uilibrium) yiel of NO2 increases (1) 7ark conse&uentiall9 on ;decreases< in (i) =e 'hatelier ar ument !ore (0)
[10]

1!.

C
[1]

1&.

C
[1]

2".

<
[1]

21.

C
[1]

22.

(a)

methyl butanoate <cce%t Aethyl butaneoate 3e?ect Lan> missin

27

(b)

the other three substances can form intermo$ecu$ar hy rogen bon s $ith themsel)es but the ester cannot. 3e?ect 8iscussion of =ondon -orces

(c) ( )

'y rolysis TJC Aust co)er a )antages an isa )antages. Aust not be contra ictory :d9anta-es to manu,acturers8 (any t1o) V not e%en ent on $eather3 seasons etc V consistent taste "concentration"more consistent V &uality V or alternati)e i eas ;isad9anta-es to consumers 8 (any t1o) V V V some %eo%le %ut off by ,nonInatural. foo may not taste the same as natural %ro uct $hich may contain other im%urities unable to escribe the %ro uct as organic

or alternati)e i eas 3e?ect cost with no ?ustification

28

(e)

4C 3 ' : COO'(l)54C' 3 O'(l)5 ?c 2 4C 3 ' : COOC' 3 (l)54' 2 O(l)5 (1) <cce%t e& subscri%ts Mo$es at e.ui$ibrium butanoic acid 2 4.4"66 2 methano$ ester (methy$ butanoate) 1ater 8.89 8.89 8.89 8.>9 6oncentration 3 mo$ dm03 (.;: (.;: (.;: 3(.:

all four e&uilibrium moles 2 (1) Conc at e&uilibrium 2 e&uilibrium moles B 8.838 (1)

(.;: (.;: ?c 2 (.;: 3(.: (1) 2 8.893 (1) ignore significant figures unless )alue gi)en to ( s.f.
The units cancel because both the to% an bottom of the fraction ha)e units of concentration s&uare . Or same number of moles on both si es of the e&uation (1) 3e?ect absence of s&uare brackets
[12]

23.

(a) (b)

Falue of e&uilibrium constant increases (1) TJC If the e&uilibrium constant increases then more %ro ucts $ill be forme (1) <n the %osition of e&uilibrium $ill mo)e to the right (1)

2
[3]

29

24.

456 <ns$er must be gi)en in a logical or er3 a terminology ressing all the %oints using %recise

V Collision ,re.uency increases as %articles mo)ing more &uickly (1) V Aore collisions ha)e sufficient energy to o)ercome acti)ation energy " more molecules on collision ha)e energy acti)ation energy (1) V < greater proportion of collisions result in reaction (1) V Collision energy has greater effect (1) V 'omogeneous all in same %hase an heterogeneous in ifferent %hases " gas an soli (1) V No nee to se%arate %ro ucts from catalyst (1) 3e?ect more collisions 3e?ect more successful collisions
[6]

30