FURTHER ASPECTS OF EQUILIBRIA

water can act as an acid OR a base , amphoteric

equilibrium in pure water :

= HzO+
-

H2O 111 t 11-20111 Laal 1- OH lag )

THE acid base

+ -

Hzo 111 = It lags +

OH lags

the equilibrium expression for the reaction is : Kc =

[H+][OH#
[ Hzo ]
•
the extent of ionisation of water is low
very
+ -

•
there is a rlly small concentration of H and OH water
in
pure

•
we can take [ Hzo ] as constant , and the expression becomes :

b
2dm
' "
( Ht ] [ OH ]
-

Kw
- -

= =
1,00 . 10 moi

↳ ionic product

of water

'

Ht [ ]
-

since [ ] =
OH
, Kw can be rewritten as kw =
( Ht ]

[ Ht ] in pure water is : [ Ht ] =
VFW =
FF =
i. no
-7
moi am
-3
 ?

Kw
=
[ Ht ]

⇐
[ Ht ) =
¥

pH calculations
-

log ,,
Few

+
the higher the concentration of It ions , the lower the pH

pH = -

log [ H+ ]
,,

pH is defined as the negative logarithm

to the base 10 Of the concentration of Ht

pH of strong acids

strong acids almost completely dissociate in solution

i. the concentration of Ht is approximately the same

as the concentration of the acid

[ Ht ] I [ acid ]

pH ( Ht ) log ( acid ]
109,0
= -
-

,,

pH of
strong bases

strong bases almost completely louise in solution

[ OH ] [ ]
-

i. base
+ -

✗ OH →
✗ + OH

to calculate the pH of strong bases , we use [ OH I

-

/ [ base 7

and kw to find [ Ht ] and hence the pH .

( Ht ] [ OH ] [Ht ] kw-
-

Kw = 1=1 =

[ ]
-

OH

pH log , , [ Ht ]
= -
weak acids

weak acids do not completely dissociate in solution , and instead

FORM an equilibrium :

Hz Ot
-

l -

g . CH COOH Lagi t H2O (l ) F lag ) t ( Hz COO lag )

z

Ht lag
-

) = t
( Hz COOH lag ) ( Hz COO lag )

↳ ethanoate ion

ka ( Ht ]lcH3 I
-

= COO

[ ( Hz ]

[
COOH

acid dissociation constant

FOR HA = Ht CA 7. ( Ht ]
-

lag ) A Laa ) t
lag ) , ka =

[ HAI

→
high value for Ka
position of equilibrium lies further

to the right , acid is almost completely

Ionised .

→
low value for Ka position of equilibrium lies fur ther to the

left acid ionised

,
is
only slightly .

p ka to strength
is used the of acids have values
compare . since some low .

pKa
= -

logy Ka
,
 calculating Ka for weak acids

we need to know :

•
concentration of the acid

of
pH solution
•
the

HA ) → A- Laal t
+

lag It lag )

+ -

when the molecule HA lonises ,

I H anion and 1 A cation are formed

[ Ht ] [ ]
-

=
A H+ arising from the ionisation of water
ignoring

ka
=
( Ht ] ( A- I =
[ Ht ]
-
-

CHA ] [ HA ]

↳ Rlglnal concentration

assumptions : of acid

•
Ht arising from the ionisation of water molecules is negligible

•
the acid is so weak that the concentration of unassociated HA

molecules at equilibrium is
approximately the same as the

original acid
 Ka =lH+
[ acid ]
calculating pH for weak acids

⇐
Litt ] =FÉ
Ka and concentration of the ace 'd
Using
?

Applying to Ka =
( Ht ]
THAT -10g , ,
FÉ
Rearranging to ( Ht ] =
✓¥A]

pH = -

10g , , ( Ft )

Indicators of acid and base titrations

indicators are used to detect the end -

point of acid -
base titrations

pH Indicator -

dye or mixture of dies that changes colour over

a certain pH Range

many pH indicators can be seen as weak acids for which the

conjugate base IS a different colour .

H+
-

Hln = + In

Un ionised
-

Indicator conjugate base

colour A COLOUR B
 •

adding acid ( Ht ) to this indicator solution shifts the equilibrium position

to the left

adding alkali 1011--1 to this indicator solution shifts the equilibrium position to

the right

•
the colour of the indicator depends on the relative concentrations of

In [ Ht ]
-

Hln and ii. e depends on

pH indicators often change colours over a pH Range of

1- 2
pH units .

ep -
9,3

ep -

3,7

between the two colour extremes there's a Recognisable end -

point

Procedure
ntat which
to monitor pH change the indicator changes
COLOUR

•
set up pH electrode connected to a computer

via data
logger
•
switch on magnetic stirrer

deliver
•
the acid at a constant slow rate into the flask

with the alkali

•
stop when the pH has reached a low constant value

can be monitored manually by recording pH after

adding fixed amounts of acid

→ the
graphs recorded on the computer / by hand show how pH varies

with the volume of acid added .

 Cambridge International AS Level Chemistry

CARRYING OUT A TITRATION (CONTINUED)

a b

RECALL

c d

16

Figure 1.15 a A funnel is used to fill the burette with hydrochloric acid. b A graduated pipette is used to measure 25.0 cm3
of sodium hydroxide solution into a conical flask. c An indicator called litmus is added to the sodium hydroxide solution,
which turns blue. d 12.5 cm3 of hydrochloric acid from the burette have been added to the 25.0 cm3 of alkali in the conical
flask. The litmus has gone red, showing that this volume of acid was just enough to neutralise the alkali.

You should note: 3 the concentration of the solution in the burette

■ all burette readings are given to an accuracy
of 0.05 cm3
■ the units are shown like this ‘/ cm3’
■ the two titres that are no more than 0.10 cm3 apart are
1 and 3, so they would be averaged
■ the average titre is 34.70 cm3.
In every titration there are five important pieces of
knowledge:
1 the balanced equation for the reaction
2 the volume of the solution in the burette (in the
example above this is hydrochloric acid)
4 the volume of the solution in the titration flask (in the
example above this is sodium hydroxide)
5 the concentration of the solution in the
titration flask.
If we know four of these five things, we can calculate
the fifth. So in order to calculate the concentration
of sodium hydroxide in the flask we need to know
the first four of these points.
 Strong acids w/
strong bases

hydrochloric acid , HCl sodium hydroxide , NaOH

3
Md dm
-
3 Mol dm
-

0,100 0,100

•
sharp fall between pH 10,5 and
pH 3,5

a small volume of Ht causes a rapid pH A

midpoint of the •
bromothymol blue changed from blue to
fall at pH 7

yellow over the

range 7,6 -
6,0 , where the

slope is the steepest

because the sharp change in

pH occurs from pH 3,5 to pH 10,5 , we can

use other indicators that

change colour within this Region .

→ indicators can be used to determine the

many end point of a
strong

acid l
strong base titration , as the sharp pH change occurs over a wide range

Strong acid with weak base

nitric acid , HN Oz ag . ammonia

0,100 mot dm 3 3
Mol
-

dm
-

0,100

sharp fall between pH 715 pH 3,5

•
and

42 6,3

pH 4,2
-

the range of and pH 6,3

methyl red changes
)
over
pH 5
midpoint
,
at
suitable indicator for this titration
-
making it a
Weak acids with strong bases

benzoic acid NaOH

3
aq . sodium hydroxide
3
,

0,100 Mol dm 0,100 mot din

- -

sharp 11
•
fall between pH and pH 715

phenolphthalein changes within the range pH 8,2 and pH 10

y
-

,
midpoints it a suitable indicator
- making

Weak acids and weak bases

Ag .
benzoic acid aq . ammonia
-
3 3
0,100 Mol dm moi din
-

0,100

•
sharp fall line
no in the
graph

•
no acid -
base indicator is suitable to determine the

end -

point of the Reaction

↳ not acceptable when 0,05 em

's

accuracy is required
 Buffer solution

a solution in which pH does not change significantly when small amounts of

acids or alkalis a re added . used to keep the pH of a solution

fairly
constant .

type Buffer
•
one of solution is a mixture of a weak acid and one

of its salts .

e ethanol acid and sodium ethanol different proportions act

-

g . in

as buffers for the

range pH h -

7 .

•
ethanol acid weak acid
staying ionised the
is a
mostly un in
-

form ( Hz COOH ,
only giving else to a low concentration of

( Hz COO in solution .

sodium ethanoate
fully ionised Solution
•
is in
aq .

solution
i .
the buffer contains
relatively high concentrations of CH z COOH and LHZCOO

µ
↳
supplies of the acid conjugate
-

reserve and its base acid

conjugate base

THE pH OF A BUFFER SOLUTION DEPENDS ON THE RATIO OF [ ACID ] AND

[ CONJUGATE BASE ]

•
In a Buffer solution , there's an equilibrium between ethanol's

acid and hydrogen ions and ethanoate ions .

 +
Adding It would
greatly lower the
pH ,
but when Ht ions are added to the

Buffer solution :

•
addition of Ht shifts the equilibrium position to the left , as Ht combines with

( COO form until equilibrium

Hz to
CHZCCCH , is re -
established

⑦
[ CH COO ]
-

large of
-

Reserve CH ,
Coo ensures ,
does not
change significantly .

large Reserve of CH z COOH ensures [ CH , COOH ] does not change significantly .

pH does not change significantly

'
. .

Adding
-

OH would great increase

pH ,
but when OH ions a re added to the

Buffer solution :

t
•
OH ions combine with It to form water , reducing [ Ht ]

equilibrium shifts to the

right
•

• t -

more
CHZ COOH molecules are ionised to form H and CH z
COO until equilibrium

is re -
established

( CH
•

large reserves of CH
z COOH ensure
,
COOH ) does not
change significantly
-
"

large ]
•
reserves of CH
z
COO ensure [ ( Hz COO does not
change significantly

:
•
pH does not
change significantly

+
F
-

log . NH
, lag ) t
1-120111 N Hy lag ) t OH lag )

+
=
Nitya lag ) Nhu lag ) t Cl Laa )
Calculating the pH of a Buffer solution

we need to know :

Ka of weak
•
the acid

- .

( salt )
of
conjugate
•
the weak acid and it base

11++1
I ,
:
=

ka .

pH pKa +

109,045¥
=

Uses of Buffer solutions

•
electroplating In humans ,
the pH of blood is

of maintained between 7,35 and 7,45

manufacture dyes
•

treatment Buffers
of leather
by various :
•

making sure
pH meters record the Right pH
•

hydrogen carbonate ions , HCOJ

plasma proteins
•
haemoglobin and

dihydrogen phosphate ( HzPOj ) and

? -

hydrogen phosphate ions ( H Poy )

1. The cells produce ( Oz result of respiration
in OUR
body as a aerobic

( Oz combines with water in our blood to form a solution containing Ht

catalysed by enzime
( Oz t H2O
- t
-
H
carbonic anhydrase -

Z .
hydrogen carbonate ions are conver ted into carbon dioxide and water as
+ H C
03
( Oz through the
blood passes through the blood vessels in our lungs , escapes lungs

If [ Ht ] increases :

Shifts
°
to the left
eg .

Ht
-

combine w/ Hcoz form CO2 H2O established

°
to and until equilibrium is re -

i. ( Ht ] is reduced and pH remains somewhat constant

If [ Ht ] decreases :

•
Shifts to the right
eq .

•
some CO2 and H2O combine to form Hoz and Ht until eg .
Is restored

i .
[ Ht ] is increased and pH is kept constant
 Equilibrium and
solubility
an equilibrium is established when an undissolved ionic compound is placed in a saturated solution

of its ions .

Rate at which 10ns Rate at which ions

=
move from the solid move from the sat .
Sol

to the sat .
Sol . to the solid

equilibrium between silver chloride saturated chloride

leg .
and a
/
silver solution

Kc
=

lAg+]lU#
IAGU ]
↳ Is )

the concentration of the solid phase is constant

[ Agtlaq ) ] /
-

Ksp
=
A Lag ) ]

solubility product
-

product of the concentrations of each ion in the saturated solution of a

sparingly

soluble salt at 298K ,

raised to the power of their relative concentrations

commoner ion effect :

reduction of the of dissolved achieved solution

solubility a salt by adding a of

a compound which has an non in common with the dissolved salt

 I

sat Aga
'

e. Sol lag )
g- .
. .

Agt
-

CSI = ( ag ) t
Agu w lag )

adding NaCl ( aa ) :

to
AGU
•
U ion is common NaCl and

left
-
•
added ce ions shift eq to the

Aga ppt
•
is

Partition coefficients

coefficient
partition : equilibrium constant that relates the concentration of a

solute partitioned between two immiscible solvents at a particular

temperature .

Kpc [XlsowentA
=

[ ✗ ( solvent B) ]

( see worked example page 319 )