I
IONIC EQUILIBRIUM 677
Ba(OHh Ba 2+ + 20H-
One molecule on dissociation furnishes 20H- ions.
The hydrogen ion concentration ofa solution So, [OIr] 2 x 10-3 M
is 0.001 M. What will be the hydroxyl ion concentration of pOH = -log [OH- ]
solution?
= -log (2 x 10-3 ) =2.7
Solution: We know that, [H+ ][OH- ] = 1.0 x 10-14
We know that, pH + pOH 14
Given that, [H+ ] = 0.001 M 10-3 M So, pH = (14- 2.7) = 11.3
14 14
So, [OIr] = LOx 10- Ix 10- =10- 11 M 31. Find the pH ofa o.002N acetic acid solution,
[H+] 10-3 ifi! is 2.3% ionised at a given dilution.
29. What is the pH of the following solutions? Solution: Degree of dissociation, a. = 2.3 =
3 100
(a) 10- M HCI (b) [Link] NaOH (c) [Link] H 2 S04
Concentration of acetic acid, C = 0.002M
Solution: HCI is a strong electrolyte and is completely The equilibrium is,
ionised.
+ H+
+C1- C(1-a) Ca Ca
So, [H+] = 10-3 M So, [H+]=Ca. =0.002 x 0.023
pH =-log [H+] log (10-3 )=3 = 4.6x 10-5 M
(b) NaOH is a strong electrolyte and is completely ionised. pH =-log [H+]
+OH- =-log (4.6 x 10-5 ) = 4.3372
So, [OH+ ] = 0.000 1M = 10-4 M 32. Calculate the pH value of a solution
obtained by mixing 50 mL of 0.2 N HCl with 50 mL of O.1N __
pOH - log (10-4 ) = 4
NaOH
As pH+pOH=14 Solution: Number of milli-equivalents of the acid
So,_ pH+4 14 orpH=1O 50x 0.2 10
Alternative method: [OH-] = 10- 4 M Number of milli-equivalents of the base
=50x 0.1=5
We know that, [H + ][OIr ] = 1.0 xlO- 14 Number of milli-equivalents of the acid left after the addition
14 of base
So, [H+ ] 1.0 X 10- = 10-10 M
10-4 = (10- 5)= 5
Total volume of the solution 50 + 50 = 100 mL
pH= log [H+] log(10-lo)=10
Thus, 5 milli-equivalents of the acid are present in 100 mL of
(c) H2 S04 is a strong electrolyte and is ionised completely. solution.
H 2 S04 2H+ + or 50 milli-equivalents of the acid are present in one litre of
solution.
One molecule of H 2S04 furnishes 2H + ions.
or 0.05 equivalents of the acid are present in one litre of
So, [H+] 2x1Q- 4 M solution.
. pH = - log [H+ ] The acid is monobasic and completely ionised in solution.
-log (2 x 10-4)= 3.70 0.05 N HCI 0.05 M HCI
So, [H+]=0.05M
Calculate the pH of the following solutions
assuming complete dissociation: pH =-Iog [H+] =-log 5 x 10-2 [log 5.0+ log 10-2 ]
(a) 0.365 g rl HCI solution = [0.70- 2] 1.3
33. What will be the pH ofa solution obtained by
(b) [Link] Ba(OHh solution. . mixing 800mL of 0.05 N sodium hydroxide and 200mL of 0.1 N
Solution: (a) Mole. mass ofHCI 36.5 HCI, assuming the complete ionisation of the acid and the base?
Concentration of HCI = 0.365 = 1.0 x 10-2 mol L-1 Solution: Number of milli-equivalents ofNaOH
36.5 = 800 x 0.05
40
HCI is a strong electrolyte and is completely ionised.
Number of milli -equivalents of HCI = 200 x 0.1 =20
So, [H+] = I X 10-2 mol L- 1
Number ofmilli-equivalents ofNaOH left after the addition of
pH = -log [H + ] = -log (1 x 10-2 ) = 2 HCI
(b) Ba(OHh is a strong electrolyte and is completely ionised (40 20)= 20
678 ('RB. PHYSICAL CHEMISTRY FOR COMPETITIONS
Total volume (200 + 800) mL = lOOO mL = llitre = 3.69 X 10- 10
20 mill i-equivalents or 0.02 equivalents of NaOH are present 37. . Calculate the pH of thefollowing solutions:
in one litre, i. e. , (i) 1.0 x lO-8 M HCI, (ii) 1.0 x 10-8 M NaOH
0.02 NNaOH = 0.02 MNaOH (Mono-acidic) and the base is
completely ionised. Solution: (i) The neutral water has[H+] I x lO-7 M
8
So, [OH- ] = 0.02 M By adding 1.0 x 10- M HCl, a concentration of 1.0 x 10-8 M
or [OH-] 2x lO-2 M H + ions has increased in solution.
pOH log (2 x lO-2 ) = 1.7 Thus, total [H+] (Ix 10-7 + lx)0:-8)M
We know that, pH + pOH=14 (lxlO-7 +[Link]-7 )M
So, pH=(l4 1.7)=12.3
=1.1 x lO-7 M
':\i· . 34. What is the hydrogen ion concentration of a
solution (i)whose pH is 12, (ii) whose pH is 5.6? pH =-Iog (1.1 x 10-7 ) [log l.1+ log 10-7 ]
Solution: . [0.0414 - 7.0]:::: 6.9586
(i) pH = -, log [H+ ] (i) The neutral water has [OW] 1 X 10-7 M
or log [H+] =-pH= 12 By adding 1.0 x 10-8 M NaOH, a concentration of
"[H+]=lO-12 M 1.0 x 10-8 M OW ions hasincreaied ins()l'ution.
(ii) pH';'; -log [H+ ] Thus, total [OW] = (I X 10-7 + 1.0 X 10-8 )M
Ux 10-7 M
or log [H+] 5.6
pOH=-log 1.1 x 10-7
or
= 6.9586
..mp.e 35. How many moles of calcium hydroxide must pH=(14 pOH)=(l4 6.9586) 7.0414
be dissolved to produce 250 mL Of an aqueous solution of pH __ 38. Calculate the S 2- ion concentration in a
10.65? Assume the complete ionisation. saturated solution ([Link])ofH 2 S whose pH was adjusted to 2by
Solution: We know that, the addition ofHCI. (Ka 1.1 x 10-21 )
pH+pOH 14
Solution: +S2-
So, pOH (14:....10.65)=3.35
[H+]2 [S2-]
[OW] = 10-335 =10--4 X 10°·65
[H 2 S]
4.47 x 10--4 M
One molecule of Ca(OH}z furnishes 2 OH - ions. or [S2-] Ka[H 2 S]
[H+]2
Hence, concentration of
Ca(OHh = 4.47 x 10--4 =2.235x 10--4 M pH 2; So, [H+] = 1 X 10-2 M
2
H2 S is a weak electrolyte, So, [H2 S] = 0.1 M
. 2.235 X 10--4
No. of moles In 250 mL 5.58 X 10-5 1.1 x 10-21 x 0.1
4 So, [S2-] 1.1 X 10-18 M
1X 10-2 X 1X 10-2
36. The pH 'ofO.1M hydrocyanic acid solution is
5.2. What is the value ofK a for hydrocyanic acid? EJ3IgpJe 39. What is the hydrogen ion concentration oj
Solution: pH = - log [H+ ] 0.1 N' CH 3 COOH solution? The ionisation constant of
CH 3COOH is 1.8 x 10-5 • What is the pH of the solution?
or log [H+] pH=- 5.2
(iTTJ
[H+] 10-5.2 = 10-{i X 10°.8 Solution: Let the degree of disso;;.: ..tion be 'a, '.
. = 6.3xlO-6 M CH3 COOHis a weak electrolyte; thus,
a, 2C Ka
'" [H+] 6.3 X 1O-{i 63 10-5 a, 2 X 0.1 1.8 x 10-5
'0;', degree 0 fd lSSOclatlOn -- = . X
C 0.1 or a, = 1.34 X 10-2
According to Ostwald'sformu1a for weak electrolyte, [H+] =a, . C 1.34 X 10-2 x 0.1 = 1.34 x 10-3 M
Ka a, 2C == 6.3 X 10-5 X 6.3 X 10-5 x 0.1 pH = -log [H+] = - log 1.34 X 10-3 2.8729
IONIC EQUILIBRIUM 679
25. Equal volumes of three acid solutions of pH 3, 4 and 5 are
mixed in a vessel. What will be the W ion concentration in the
mixture? [CBSE (PMT) 20081
19. At 90°C, pure water has [H30+] == 10-6 M. What is the (a)3.7xlO- 3 M (b) 1.11 x 1O- 3M
value of Kw at this temperature? [CBSE (Med.) 2006]
(c) 1.11 X 1O- 4M (d) 3.7 x 1O- 4M
(a) 10-6 (b) 10-12 (c) 10-13 (d) 10- 14
[Ans. (b)] [Ans. (d)]
[Hint: [H+] 1O-3M, [H+]== 10- 4 M, [W] = 10- 5 M for the
[Hint: [HP+ ] = [OH-] 10-6 M
given acids .
., Kw=[HP+][OH ]=10- 12 ]
MmixVmix MIV I + M 2V2 + M3V3
20. The pH of 0.5 M aqueous solution of HF (K a == 2 X 10-4 ) is: M mix X 3 10- 3 X 1 + 10- 4 X I + 10- 5 X 1
(a) 2 (b) 4 (c) 6 (d) 10 5 5
M 10- [100+10+1] l11xlO- . 37xl0- 5 M
[Ans. (a)] mix
3 3
[Hint: [W] = x 2 x 10-4 = 10-2 M = 3.7 X 10- 4 M]
pH = -Jog io [H+] log 10-2 = 2]
21. The hydroxyl ion concentration in a solution having pH value BUFFER SOLUTIONS
3 willbe:- For several purposes, we need solutions which should have-
(a) 10- 11 M (b) 10-7 M (c) 10-3 M (d) 10- 14 M constant pH. Many reactions, particularly the biochemical
[Ans. (a)] reactions, are to be carried out at a constant pH. But it is observed
[Hint: pH + pOH 14 that solutions and even pure water (pH = 7) cannot retain the
pOH 14 pH == 14 - 3 == 11 constant pH for long. If the solution comes in contact with air, it
[OW]= 1O-poH 10- 11 M] will absorb CO 2 and becomes more acidic. If the solution is_
stored in a glass bottle, alkaline impurities dissolve from glass
22. A 50 mL solution of pH 1is mixed with a 50 mL solution of and the solution becomes alkaline.
pH = 2. The pH of the mixture will be nearly: A solution whose pH is not altered to any great extent by the
(a) 0.76 (b) 1.26 (c) 1.76 (d) 2.26 addition of small quantities of either an acid (H+ ions) or a base'-
[Ans. (b)]
(OH - ions) is called the buffer solution. It can also be defined as a
[Hint: pH = 1, [H+ ] 10- 1 M
solution of re!)erve acidity or alkalinity which resists change of pH
pH = 2, [H+] 10-2 M
upon the addition of small amount of acid or alkali.
MIV I + M 2V2 MR(V j + V2 )
10-1 x 50 + 10-2 X 50 MR X 100
General Characteristics of a Buffer Solution
(i) It has a definite pH, i. e., it has reserve acidity or
MR 5.5 X 10-2 M
alkalinity.
(Resultant molarity of H+ ions) (ii) Its pH does not change on standing for long.
pH -log 5.5 x 10-2 = 1.26] (iii) Its pH does not change on dilution.
23. The pH of a solution obtained by mixing 50 mL of 0.4 N HCI (iv) Its pH is slightly changed by the additiori of small
and 50 mL of 0.2 NNaOH is: quantity of an acid or a base.
(a) -log 2 (b) log 0.2 (c) 1 (d) 2 Buffer solutions can be obtained:
[ADS. (e)] (i) by mixing a weak acid with its salt with a strong base,
[Hint: N J VI acid - N zV2 base NR (VI + V2 ) e.g.,
(a) CH3 COOH + CH 3 COONa
0.4 X 50 - 0.2 X 50 NR X 100 (b) Boric acid + Borax
NR 0.1 (c) Phthalic acid + Potassium acid phthalate
[H+] [Link] (ii) by mixing a weak base with its salt with a strong acid,
e.g.,
pH -Jog [W ] = -log 0.1 == 1] (a) NH 4 0H + NH 4 Cl
24. What will be the pH value of 0.05 M Ba(OH)2 solution? (b) Glycine + Glycine hydrochloride
[PMT (Raj.) 20061 (iii) by a solution of ampholyte. Theampholytes or
(a) 12 (b) 13 (c) I (d) 12.96 amphoteric electrolytes are the substances which show properties
[ADS. (b)] of both an acid and a base. Proteins and amino acids are the
[Hint: Ba(OH)2---7 + 20ft examples of such electrolytes.
0.05 M 2 x 0.05 M
0.1 M
pOH = -log [Oft] == -log 0.1 == 1
pH=14 113]