Hence the solution of ammonium acetate would be neutral .

. 13 THEORY OF ACID-BASE INDICATORS

e acid-alkali titrations, the equivalence poin't is detected by the use
ators which change their colour at or near the equivalence point. Au!
nic acid or a base which possesses one colour in acid solutions
ine solution. The actual colour that it produces in solution d ~ s
e in colour of the indicator is not sudden and abrupt but .t81C~
is called the "colour change intervaf' of the indicator.1.el
ators work.
(,) Ostwald Theory: The first
indicators are regarded as
n or the basic indicator f
The ion1z1ng equd1bn

and
 Kind l

[H30+]-K l 1
md bn)

[ H3o•] = K md
(unionized fonn]
[
ionized form]
In acid solution presence of exc~ss of H3Q+ ions wdl suppress the •o•
and [In-J will be small_. The col_ou~ wt!I therefore be mainly due to the um
d in alkaline solutions the 10mzat1on equilibrium is shifted to the ngbt
han . . .
f ionized form In-. Hence m alkaline medium the indicator will exist
~ie colour of the ionized form_ be_comes apparent.
The actual colour of the md1cator depends on the ratio of the conce
unionized forms, and is thus directly related to the hydrogen ion concentra
(14.56) may be rewritten as

hn-1
pH = pKind + log [Hin]

For a base indicator, an exactly analogous expression may be deduced

In+
pOH = pKmd + log--
lnOH
At any given pH of the solution, both forms of the indicators will be
realise that the human eye has a limited ability to detect either of the two co
[IDn]
predominates. In general, when [In-] = 10, Eq. (14.57) reduces to

pH= pKind -1
_and the colour of the solution will appear to be due to the unionized fonn

I0, Eq. ( 14.57) reduces to

pH= pK,nd +1
 tI • pJ > 0Ju11 n
1
[ ~: ] hcrnmc unity and the nd1ca10 w,11 h

<.I and base f 01 ms.. This 1s sometimes c lied as th · middl

1lll) Jf the two coJours a1e of equal intensity.
(11) Qutnonoid Theory: The colour in most of the natunlJy occ.:u
t hutcd to be due to the presence of quinonoid structu1c.

Oulnonoid structure
(coloured)

A theory called quinonoid theory based on this observation was put forward to
m colour of indicators with pH. According to this theory, the colour changes are be 1
stmctural changes including the production of the quinonoid and resonating foml$
trated by reference to phenolphthalein where (/) represents the structure of p
the presence of dilute alkalis changes to structure (//). This triphenyl carb1no
typical loss of water, then yields a red resonating di anion (III). If phenolp
of concentrated alcoholic alkalis the red colour first produced di
carbinol form (IV).

0~ rYOH

~;J
6-L
 N-N
I
H

Methyl orange m presence of acids

(Quinonoid structure-red)

Table 14.5 contains a selected list of some indicators along with their colour c

Table 14.5 Some Indicators and Their Characteristic pH Ranges

Indicator pH range Colour ,n

acidic solution

Cresol red 0.2-1.8 Red

m-cresol purple 1.2-2.8 Red
Methyl orange 3.1-4.4 Red
Methyl red 4.2-6.3 Red Yellow
Phenol red 6.8-8.4 Yellow Red
Cresol red 7.2-8.8 Yellow Red

Thymol blue 8.0-9.6 Yellow

henolphthalein 8.3-10.0 Colourless
lizarin yellow 10. 1-12 1

By suitably mixing cerwn

ange. Such a mixture is
e approximate pH of
thymol blue and
nt pH value& as
 of a Strong Acid by a
allalli added dunag the titration
UtiOn starts
sharp nc
e in pH is small on
cons der the tra ·on of I 00 m
the end po nt ·1 ·s seven.

=a
70
 1
(1.0 mol L )

(190 ml) (IO ml)= S.26 x 10-2 mol L 1

J the pH 1.3.
is + .
The i:onccntra(Jon of H"O mns and pH values during the course of titration are
able 14.6. . .
From the table 14.6 1t 1s apparent that between 99.9 ml to 100.1 ml of alkah
lution rises sharply from 3.3 to I 0. 7. Hence any indicator with an effective range
~.5 rnay be used. Conscque~tly, both_ phenolp~thalein (pH range 8.3-IO.O) and
l t--4.4) may he used. If the solutions are dilute to 0.0lN, change in pH and the
ngc- . 1· . d H
e less sharp and the range is im1tc top 5.5-8.5. Indicators such as methyl red,
111 be !'latisfactnry.

Table 14.6: pH During the Titration of I 00 ml of IN HCI with l N NaOH Sol

Volume 4 alkali added (m/) I H_p+ }, mole/litre

pH
0.0 1.0 0.00
50.0 3.33 X 10-I
0.48
75.0 1.43 X lQ-I
0.94
90.0 5.26 X 10-2
1.30
98.0 1.0] X 10- 2
2.00
99.0 5.03 X J0- 2 2.30
99.9 5.01 X 10-4
3.30
100.0 1.00 X 10-7
7.00
100. l J.995 X ]0-I I
100.2 1.00 X JO-II
100.5 3.98 X 10- 12

n of a Weak Acid by a Strong Base: Consider the titration of 100 ml of,

lution. The initial pH of the solution is not one as the acid 1s only'.
acid is the only species present, pH of the solution can be calcul
d to the acid solution, sodium acetate is formed and the mix
as a buffer. The pH values up to the equivalence point can be

[salt]
pH= pKa + log [ . ]
acid
s of the salt and the acid may be calculaled
-~-w JOO ml of O IN acetic ac1d hlaon.~~r-,,:-
 pH 4'
430
l'hetef~ the pH 4 3 When half of the acid bas
•
7
been neutralized alt and acid concentrati.ons are equal
and the pH is equal to pK (4 73 The pH at lhe ~ • a
1ence pomt wdl not be seven due to hydroly . of Cfl,COO-
ons The pH value at the equivalence point can be calcu i 5
ated COOSJdering the hydrolysIS of CH COO- ions usmg
Eq 14 SO)
.
3
I
pH=
2 pK + pK0 +logC] 2

= ~ ((14) +(4.73) + (2.699)]

=8.72
Fig. 14.2 Dalfllii
After the equivalence point excess of OH- ions will acetic acacl w1111••
suppre s the hydrolysis of the anion and pH is then solely
dependent on the concentration of OH- ions provided by the added NaOH. 11ae
g ven m Fag. 14.2 and the pH values at different stages of titration are given•

Table 14.7 pH Durmg the Titration of I 00 ml of 0.1 N Acetic Acid by

Volume of aJJ,.,a/1 added (m/) {H,o•J, moleA,tre

00 1.260 X 10-2
250 S 012 x I 5
soo I
900
9
 . e,~.1r) to u ... c an indic.ll<'.r "ith a pH range slightly on alkaline ~idc. Hence the commonl" d
nee., • 111ic;nol1Jhlhalein or thymol blue A · l . . ., use
ind1caro1!> .in.: . . . . ny me. icalor changing it~ colour below pH 8 wall be
. f,}don·. Cnmpanng the pJot 1ll F1g. 14.2 with that in Fig 14 1 we see lhat. th' h b
ull'·i11, ~ .. . 1 • . 1 · • • · rn 1s ca5e t e c ange
cnc-c point IS css sharp. For weaker ·1cids like HCN Cle H h
r 11.1 1ic:r• thl' t?l]lllVa
1

Ifl , 1, 11 c<! point bccnmc sldl

•
lcbs pronounced. • • • ., p c anges near the
l•qLJ1\.ll • '·kB h . ' .
,,·) Titratwn of a \\ea_ ase Y a Str?n~ Acid: Consider the titration of 100 ml of O.IN NH
. 11 by n. IN HCI solu11on. When no acid 1.s added the pH value is calculated uc-ing
-ol,ut10 .... Eq . (l
~ 1·. ,11 or HCI prnduces
Acllilll . the salt, . NH-1CI and the mixture of NH ~ and NH J CJ 'tcts
( as a buffer
4
and11'1
r1H vdlLIL' ur to Lile equivalence point can be calculated using the Henderson Eq. (14.37)
[salt]
pOH = pKh + log---
[ base]
At ihc equivalence poinl the solution contains the salt and the pH of the solution is determined by
the hytlrolysis of NH; ions using Eq. (14.44).

1
pH=
2 [PKw - pKb - log C]

= ~ [(14) - (4.73) -(2.699)] = 5.29

Thus the pH at the equivalence point is 5.29. Beyond the equivalence point addition of HCI sup-
sses the hydrolysis of the salt and the pH is controlled by excess of H 30+ ions from HCI. The pH
ues at different stages of titration arc given in Table 14.8 and the titration curve in Fig. 14.3. TIie

12

11

10

I 6
0.

Fig. 14.3 1 Hrat,on of 100 ml of 0.1 N ammo.tlltam:

 Tlic pH at the equivalence point is calculated by using Eq. _
14 55
1
pH==-[pK
2 ¾
+pK11 - pK]
h

~ [(14) ➔ (4.74) (4.74)]

= 7.0
T he main fratur~s
.
of th~ titration curve is that the pH ch·
. ., , . . , .
d .
angcs urmg the entire
tratil1n arc gradu,11: ~cn_l:c -~o s~a1 p ~nd point can be ohtained with the commo ly
rs. Howe\ er, a mixed rn~1ca1_01 which shows a sharp colour change over a hmtted
mctimrs be used. In t!1c tllrallon of ammonium hydroxide hy acetic acid, neutral red
dicator may be occas1onally used. Such titrations arc usually avoided.

4.15 SOLUBILITY PRODUCT

a sawrated solution of a sparingly soluble salt, a dynamic equilibrium exists between
It and its dissoci ated ions. For example, a salt like AgCI when added to water, a ma
•s into th e solution yielding Ag+ and c1- ions and the rest remains as excess solid So
equili brium with Ag+ and c1- ions. The equilibrium may be represented as
AgCI (solid)~ Ag+ (aq) + CJ- (aq)
r wh ich we can write

K = a Ag+ ac1 -
aAgC1

The acti\ity of pure so lid AgCl may be taken as unity and hence we can write

Ksp = [a Ag+][ act-]

ere K is known as the solubility product ofAgCl and is defined as the product of the
ti
n lll saturated wlution of a sparingly soluble salt. Since the salt is sparingly
n is d1 ute and hence th e activities of the ions may be replaced by the correspoindiDJ
Equauon ( 14.60) can then be written as
K sp = [Ag+ ][cl ]
y r uct i& dependen t on temperature and is nearly independent < f
r J p >vide<l the ~olution js diJute. In the case of ,tn msoluhl s
ffi t in the disliochtinn cquillhtium a1e not cqu I lo u 11 '
Cal (,) Ca • (,1q) t I ( q)
Th~ K,, < Ct · the n !IV n hy

tlence the solubilny product conD-..,.••