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rname names

Centre Number Candidate Number

Chemistry
Advanced
Ko. K6 K,-pAJ
I - Rates,
Unit 4: General Principles of Chemistry-Chemistry
Equilibria and Further Organic
(including synoptic asses-ment)
Paper Reference
03 Saturday 03 October 2015 -Afternoon
Time: t hour 6CH04lOL
You must have: Data Booklet

Candidates may use a calculator.

Instructions
Use black ink or ball-point pen.
Fill in the boxes at the top of this page with your name,
centre number and candidate number.
Answer all questions.
Answer the questions in the spaces provided
- there moy be more spoce thon you need.
Information
The total mark for this paper is 60.
The marks fbr each question are shown in brackets
- use this os a guide as to how much time to spend on each question.
Questions labelled with an asterisk (*) are ones where the quality of yoru
written communication will be assessed
- you should toke particulor care with your spelling, punctuotion and grammor, as
well os the clarity of expression, on these questions.
A Periodic Table is printed on the back cover of this paper.

Advice
Read each question carefully before you start to answer it.
Keep an eye on the time.
Try to answer every question; ,:
Chesk your answers if you have'time at the end.
Turn oveft"
iii.u ,
! \i.i .:

,p;tl
7
't
',ud'
18 Ethanedioic acid, HrCro* is a dicarboxyric acid which
example in rhubarb learies, and is occurs in many prants, for
,sed u, a rust r.rou., and strong descaler.
structure of ethanedioic acid is The
shown below.

oo,
ltil
H_O_c_c._o_H
Ethanedioic acid isa much stronger
acid than carboxyric acids such as
l:_"].n
pI o{ 1.38. The hydrogin_ethirnedioar. ilr,'Hcrq-, ethanoic acid,
?. is a weaker acid than
ethanedioic acid, having a px"if +.28,
although rrightiv stronger than ethanoic
acid.
(a) (i) write an equation for
the reaction of the hydrogenethanedioate
water to form an acidic solution. lnclude ion with
riute ivrloit iri v",i,.
"q"uation. (z',)

(g) r )ou=-A
ue'o'l
C^OI- + H oot
v
P) @')

(ii) write the expression for the

acid dissociation constan! K., of the
HC2O4-. weak acid,

(1)

l<a --
_-t
U e rol ),

ilflilililil ililililil Iilil ilililililI ilfl ililililil ilIil ilililil illl

I lllililt ilr il] ilIIffiil ffiil ililil ilffiil 1ilil llilillllt ]lt lilt
 (c) 2s cm3 of a 0'050 mol dm-3
solutionof sodium hydrogenethanedioate
with a sodium hydroxide sorution of the was titrated
same concentration.
(i) On the axis below sketch the. curve
for this titration.
(3)
14

12

10

8
pH
6

9,? 07

'o t3
Voluine of NaOH / cm3
*(ii) when 25
cm3 of a 0.050 mol dmr solution of ethanedioic
acid is titrated with
sodium hydroxide solution of the same concentration
using phenolphthalein
as the indicator, the end point is 50
cm3.

when methyl yellow indicator is used, the colour

changes at around 25 cm3.
using the information given at the start
of the question and quoting data
from page 19 of your dlta bookle! suggest
why these volumes are different.

gs&rforggs$ig-Ll8 = 15 marks)

(^" a#'J e'D ilra//, lL e"d pinl uou_lJ [.,,uor, V

I ilililt til ilIil ililt lilil ililt ililil ilil illl ilil ililt ililt tilt fft
 1S (a) Calculate the pH of 0.25 mol dm-3 hydrochloric acid.
(1)

Pft - -b4tr1 :-wE*J: o,60 L otLO,6O

(b) Propanoic acid, CH3CH2COOH, is a weak acid with Ko:1.3 x 10-5 mol dm-3
at25"C. ph = -tgQox,6) cl.gg on use
=
(i) Write the expression for Kufor propanoic acid.
(1)

ka: cltscoot+ + ct+3cwtao fi+

l#s&f:*1
(ii) Calculate the pH of 0.25 mol dm-3 propanoic acid at 25oC.
Q)
pu"arro")Bt - Ka X far"coou]
) C"t-
of 0.25 mol dm-3 propanoic acid.

(i) Write an equation for the reaction which occurs. State symbols are no, t.Ottt.U.,r,

i
cfiscHzcooH + Na1ft ctbcHzcoofa + Hzo

i --$lt this point the titration mixture contains 1.5 x 10-3 mole! ilgopanoic acid StiJfi-
i:d.S=' *@olesofpropanoateion. @ iobtru'
. Nog,n vr"ffi#ilHrt* for K" for propanoic acid to calculgte the pH of the mixture.
.V cc'ir'4rr'!'*'lad'r'son-Hrc'lLa%A rco&

uto=
e
kg noulc.,
^:"""1r
'?lj:' |

^., il?H:l:^)i-"ffiu
=-LZQtr,-f)+%ffi
-

ffito-l
L) = l,BB - o'L*6
+ pH ='1,70E9es1 orc'!.7 T {=t1,7
I ililil iltllilt illllllll llll llllllllllillll lllll lllll lllll lll llll
 +(iii) When a further small amount of 0.10 mol dm-3 sodium hydroxide is added in
the titration, the pH changes very little. Explain why the pH change is small.

llu ,nfxlurrc ,f CtbCH2emH mtd NaAtI

6iues
a* butJensolefi:dn
/l o s*al/ arnaunt of rvala Grc ou-l on -bos) is oddd t" u h*f!*
solil+i'on, fIQu) cambfnes uitlh acid
dissrciated prcotmfut) J""mirg HaO,
CHyCH 2CaoH dissocr"a/.s G?pUb nium
sh',/kl,lh,"lil0t-i1ttu-P-kela'kW
d ttt ,t h"![ro.'"oll'rhsn wnkins b'JJ'"iru rnixh.urz-'

hu6* crrrra,nt t ol- undissaalald ocld

'
(iv) Draw the titration curve showing the change in pH when 0.10 mol dm-3 sodium
hydroxide is added to 10 cm3 of 0.25 mol dm-3 propanoic acid until present in
excess. The equivalence point is 25 cm3.

& fr) uS
e+.rcl
!i"i* ^l n +- u'l)a
trr,h'*l neqig't
J;;.,,? "9;d
'rntd rpirl. is aLrlte10
;"&,:;ba,

10 20 zs 30 40

Volume of sodium hydroxide solution/cm3

r llilil ilr lllll lllillll lllll llllll llll llll lllll lllll lllllllll llll
 (v) Explain, referring to your data booklet, whether bromocresol green would be a
suitable indicator for this titration.
(2)

ok pko +t b.
izr fhr v.efthca( rcegbn (s,r +o- D
musl
5o brrorrtxffi&sal grct=n is nab suiln'bL ot pKll = *1'7 ,

(d) Propanoic acid is produced in the reactions shown below.

CH:CHzCN Reaction I

Reaction 2
cH3cH2cocl CH3CH2COOH

Reaction 3
CH3CH2CHO

(i) Suggest a reagent which could be used to carry out reaction 1'.
(1)

(1)

cucfizcocI + llzo + ellscfrzeooil + Hcl

(iii) What would be observed if reaction 3 was carried out using potassium
dichromate(Vl) and sulfuric acid?
(1)

Colou o eryte', dtnrcn)l arcaln1* +.- 6rreEn :

I ilil|] llilllll llil lllll lllll llllll llll lllll lllll lllll lllll llll llll
I

(a) Methanoic acid, HCooH, is a weak acid. Explain what is meant by the terms
weak and acid.

fr v{k.a-K'.. or;d...... dtssaetnl.*s... h..a.. uetJ.... srna / [ ., *frrL .

An.. Aet.d ....fe a. pnalor] .d,ono.rc

(2)

(b) Write a balanced equation, including state symbols, for the reaction between aqueous
solutions of methanoic acid and sodium carbonate.

2#A0HW) r Na/:)s@* %Heoo*o@ t (8-1^:

(c) The following equilibrium is set up when methanoic acid dissociates in water:

HCOOH(aq) + HzO(l) <+ HCOO{aq) + H:O*(aq)

(i) There are two conjugate acid-base pairs in the above equation.

Identify them by completing the sentences below:

Formula of one acid is ilcooft

(1)

Formula of the other acid is TbAT

 (ii) Write the expression for the acid dissdciation constant, K, for methanoic acid.

K: pcooul
(1)

(iii) calculate the pH of a 0.100 mol dm-3 solution of methanoic acid at29gK.
[K for methanoic acid is 1.60 x lOa mol dma at 29g K] _I

Uuo! F.oo-] = K^EorD -;,if=:-:nt'6xtD

+
[t rJ':
xofrcoo]il reo1 =E
)furt=
i L- r v\ / \ / P
ror* = voyt;'QotO u==urGBo-ro6c,-rlj It'=+(!ka-,z,=4)
l" gH 2'Llo I -,r,
i2
'.1
= L pH
=-2,io
(d) A buffer solution is made up by mixing equal volumes of 0.100 mol dm-3 methanoic
i
acid and 0.400 mol dm-3 sodium methanoate.

tt, *t'urate the pH orthe burrer

rc',o,r)-
oou*.
--- : ::iitui"d'
JYed[! @
ffiffi=taffift {=eh*t06ffi
/ : $'80 + loq to'qoil
h'l = L6xto't ,E''oo\ ll C E, J
;J ^ b'qoo] ^,* Ll,qO'ta
ll pll
=
FI
pH : L'l'4 o
 (ii) Explain why the pH of this mixture of methanoic acid and sodium methanoate
remains almost constant when a small quantity of an acidic solution, containing
hydrogen ions, or a small quantity of an alkaline solution, containing hydroxide
ions, is added.

In your explanation include equations to show the effect of adding hydrogen ions
and of adding hydroxide ions.

H C.O.O H ... .o/rtd ......... H.C.o.a Na-......rnake,s. a huIJere

HCO>H + H{ 77 Hcoo- + HsOn

i
A ,bu!!en .soli frrn.
I
I
i
I
I
I
I

rcffi*s- uifuh sall

I
t

) * *"?n.... und
j

xdatrl aeid
i
I
t
I
J.issocialrl^..an ion @ co a i.ss.
I

:i

i
I
)

i
i
I
I
i

i
I
l
l
t

@rr"la)
Ori d;tal;'n f|a nnhu
ffi naff;t#I/ rc;

iK,i j3 qn;o{lr" consH.f. 4#;;- n.u.<";p J/,-6;

l'o,n rceynaints
"olffui?t.q,r: 16 marks)
 (a) The first step in the esterification of ethanoic
acid, CECOOH, by ethanol in the
presence of a small quantity of concentrated sulphuric
acid, is the reaction

CH:COOH * HzSOq _+ CH:COOHz* + HSO+-

basa aeid c.'{, acid coryu'a!3ase-

In the space below the equation, identi$r the two acid base conjugate pairs.
(2)

(b) Ethanoic acid, CH:COOH, is a weak acid and dissociates

in water according to the
equation

CECOOH(aq) + HzO(t) e+ H:O*(aq) + CH:COO-(aq)

Its acid dissociation constant, Ku, is

6"= [Hol [cHrcoo-] =r.74xrosmol dm3(at 25.c)

lcH3cooHl

(i) The concentration of a solution of ethanoic acid can be determined

by titrating
a25.0 cm3 sample in a conical flask against a standard solution of
sodium hydroxide.

State whetler the pH at the end point is less than '7,7, ormore than 7 , andhence
name a suitable indicator for this titration.

pH at end point ...,..m0.1fe lhan-.7

Indicator . .
p.hene.tpl.llr.olr:n. ...(...r,.r.. .Ie. Lg)
(2)

(ii) Ethanoic acid is only abou-]t% ionised in dilure solutions. Its enthalpy
of
neutralisation is -55 kJ mol-r, whereas the enthalpy of neutralisation of
a strong
acid, such as hydrochloric acid, is kJ mol-t.
-57
Explain why there is so liule difference between these two values.

shrf{s te lhe *fSAt as a rL*sull all

(3)
l2
 (iii) Calculate the pH of a 0.140 moldm-3 solution of ethanoic acid, clearly showing
the TWO assumptions that you have made.

Calculation
re:
r'A Eu+o0741
-
*ut z-
6

roEbeDcx)
b6coo!]
Hrrdercsun - tlass.l
t- -rL
ro t) ^@,rlo) Ptr=+-G^-*BG",A)
=> LHI Gzqx
Ptt
=) PH = 2,8O
Pl+ = 2,gO

(4)

(iv) To 50.0 cm3 of the solution in (iii), an equal volume of a 0.200 mol dm-3 solution
of potassium ethanoate was added. Calculate the pH of the buffer solution
- obtained.
Ka rcou|. H rntrl rgsn - llass. I balc|

t-i] = r^ffi
bwropil
EHrtoo-
pft
= pl.o *tzffi
PF= -tg '?1xtr5 + rAffi
B' = €.?,1x,;)"
r

-n L'ZZ\65
?H: tt,76 + o.75
0t
PH: q,9L
Pl+ = q'9L
(3)

(Total for Q:4 = 14 marks)

END
Total For The Paper = 60 Marks