pH of weak acids:

 A small quantity of weak acids is dissociated with the formation of

H+ eg. CH3COOH HAC AC- + H+

 Where: [H+] = [AC- ] and [HAC] = Ca (concentration of acid)

[H+]2 = KaCa
[H+] =  KaCa = Ka0.5 Ca0.5
pH = ½ pKa + ½ pCa
 Examples
 Calculate the pH of 0.1M solution of acetic acid (Ka = 1.75 x 10-5)
pH = ½ pCa +½ pKa
= ½ ( -log 0.1) + ½ (-log 1.75 x 10-5)
= (0.5 x 1) + (0.5 x 4.757) = 2.88
 Calculate the pH of 0.25M solution of formic acid (Ka = 1.76 x 10-4)
pH = ½ pCa +½ pKa
= ½ ( -log 0.25) + ½ (-log 1.76 x 10-4)
= (0.5 x 0.602) + 0.5 x 3.754
= 0.301 + 1.877
= 2.18
pH of weak bases:
 Weak bases is slightly dissociated with the formation of OH-
ions. BOH B+ + OH-

[OH-]2 = KbCb
[OH-] =  KbCb = Kb0.5 Cb0.5
pOH = ½ pKb + ½ pCb
pH = pKw – pOH
pH = pKw – ½ pKb - ½ pCb
 Examples
 Calculate the pH of 0.1M solution of NH4OH (Kb = 1.8 x 10-5)
pH = pKw - ½ pKb - ½ pCb
= 14 - ½ (-log 1.8 x 10-5) – ½ ( -log 0.1)
= 14– (0.5 x 4.745) – (0.5 x 1)
= 14 - 2.87 = 11.13
 Calculate the pH of 0.025M solution of NH4OH (Kb = 1.8 x 10-5)
pH = pKw - ½ pKb - ½ pCb
= 14 - ½ (-log 1.8 x 10-5) – ½ ( -log 0.025)
= 14– (0.5 x 4.745) – (0.5 x 1.602)
= 14 – 3.17 = 10.83
 pH of Salt Solutions
 Salts of strong acids and strong bases e.g. NaCl is neutral
pH = 7
 Salts of strong acids and weak bases e.g. NH4Cl
pH = ½ (pKw – pKb+ pCs)
 Salts of weak acids and strong bases e.g. CH3COONa
pH = ½ (pKw + pKa - pCs)
 Salts of weak acids and weak bases e.g. CH3COONH4
pH = ½ (pKw + pKa – pKb )
 Buffer Solutions
Buffer solutions are solutions which resist the change in
the pH of solution upon addition of small amount of strong
acid or strong base.
Types of Buffer solutions:
There are two types of buffer solutions
1-Acidic buffer
2- Basic buffer
 1-Acidic buffer
 Consists of weak acid and its salt of strong electrolyte.
e.g. Acetic acid and sodium acetate (CH3COOH / CH3COONa)
 Upon addition of strong acid (H+):
sodium acetate reacts with it giving weakly ionized acetic acid.
H+ + CH3COONa → CH3COOH + Na+
 Upon addition of a base (OH-):
acetic acid reacts with it and non ionized water is formed.
OH- + CH3COOH → CH3COO- + H2O
 2- Basic buffer
Consists of weak base and its salt of strong electrolyte, e.g.
Ammonium hydroxide and ammonium chloride (NH4OH /
NH4Cl)
Upon addition of a strong acid (H+):
NH4OH reacts with it and non ionized water is formed
H+ + NH4OH → NH4+ + H2O
Upon addition of a strong base (OH-):
NH4Cl reacts with it giving weakly ionized NH4OH.
OH- + NH4Cl → NH4OH + Cl-
 Calculation of pH of buffer solutions
 pH of acidic buffer:

pH = pKa + log Cs / Ca
 pH of basic buffer:

pOH = pKb + log Cs / Cb

pH= pkw - pOH

pH = pKw – pKb – log Cs / Cb

 Examples
 1- Calculate the pH of a buffer solution consists of 0.1 M
CH3COOH and 0.1M CH3COONa (pKa = 4.7)
pH = pKa + log Cs / Ca
pH = 4.7 + log 0.1 / 0.1
pH = 4.7 + 0 = 4.7
 2- Calculate the pH of a buffer solution consists of 0.07 M
NH4OH and 0.28 M NH4Cl (pKb = 4.7)
pH = pKw -pKb - log Cs / Cb
= 14 – 4.7- log (0.28 / 0.07)
= 14 - 4.7 - 0.6 = 8.7
 Neutralization Indicators
 Neutralization indicators: are substances that change their color
according to the pH of solution.
 They have different colors at different pH values.
 The change of color is not sudden but takes place within a small
interval of pH (2 pH unites or less). This interval is called color
interval of the indicator. (M.O: 3.3 – 4.3 & ph.ph: 8-10)
 It is best to select an indicator which exhibits color change at pH
close to that of end point.
 Types of Neutralization Indicators
1- Color indicators:
 Organic dyes which exhibit different colors at different pH values.
a-Tow color indicator: eg. Methyl orange “M.O”
Color change from red to yellow or orange
b-One color indicator: eg. Phenolphthalein “ph.ph”
Color change from colorless to pink
2- Turbidity indicators:
 Turbidity or ppt appears or disappear at desired pH (the end point.)
3- Fluorescence indicators:
 Formation or lose of fluorescence at desired pH (the end point.).
 Theories of color indicators:
 A- Ostwald theory:
 Neutralization indicators are either weak acids or weak bases.
 The color of ionized form different from that of non-ionized one.
 In acidic med. basic ind. is ionized and change its color e.g. M.O
InOH (Yellow) In+ + OH- (Red)
 In basic med. acidic ind. is ionized and change its color e.g. ph.ph.
InH (Colorless) In- + H+ (Pink)
 Net of color of the indicator depends upon the ratio of the ionized to
non-ionized parts which decided by the [H+] in the medium.
 Objections against Ostwald theory
1. For ph.ph.; (colorless, pH < 8) addition of small alkali causes color
change to pink (pink, pH 8-10) and addition of more alkali causes
disappearance of color (colorless, pH > 12) while as expected from
the theory the color should increase.

2. Color change is slow while ionic reactions are instantaneous.

3. Some acid base indicators exhibit their color change in non

aqueous medium where ionization is markedly depressed, this
means that, there is no difference between ions and molecules.
 B- Chromophore theory:
o Neutralization indicators are organic dyes which contain an
unsaturated group called chromophore group e.g. N=N-, C=C,
N=C which responsible for the color.
o When the indicator accept or donate proton, rearrangement of
the bonding in molecules takes place leading to the color
change.
o The color change is not due to ionization alone but also due to
tautomeric changes in the structure of the indicator.
e.g. Methyl orange (basic indicator)
Ph.ph in acid medium has lactone structure which is colorless
while in basic medium has quinone group (chromophore).

OH-

H+

In acid medium ph.ph. has lactone In basic medium ph.ph. has quinone
structure group (chromophore)
(colorless ) (pink color).
 Effective range of color indicator:

o It is the pH units over which the indicator changes its color.

o Within this range the color change will be gradual.

o For a good indicator, effective range should not exceed 2

pH units (M.O: 3.3 – 4.3, methyl red: 4-6, ph.ph: 8-10).

Mixed indicators:
o Mixture of two indicators having similar pH range but showing
contrasting colors to make the color change more sharp.
o e.g. mixture of thymol blue with cresol red.
Screened indicators:
o Mixture of an indicator with a pH sensitive dye to produce more
sharp color change.
e.g. mixture of M.O. and Indigocarmine, the color change from
yellowish green (basic) to violet (acidic ).
The use of screened ind. make the color change more sharp and
pronounced.
Universal indicators:
 Mixture of certain indicators, it exhibits different colors at
different pH values.
 Universal indicators are not used for quantitative analysis but
used for rough determination of pH of solution.
e.g. bromothymol blue and ph.ph mixture it gives:
red color at pH 2, orange at pH 4, yellow at pH 6, green at pH 8
and blue at pH 10.
 Neutralization Titration Curves
 Titration curve of strong acid against strong base
e.g. HCl against NaOH HCl + NaOH → NaCl + H2O

 1- pH at beginning is pH of strong acid:

pH = -log [H+] = pCa (Initial acid concentration)
 2- during titration: pH = pCa (from the remaining)
 3- at e.p.: pH = pOH = ½ pKw = 7
 4- after e.p.: pH = pKw – pCb
So that, both M.O. and ph.ph are useful.
Titration curve of weak acid against strong base
e.g. CH3COOH against NaOH
CH3COOH + NaOH → CH3COONa + H2O
 1- at beginning, pH of weak acid;
 pH = ½ pKa + ½ pCa
 2- during titration, pH of acidic buffer;
 pH = pKa + log Cs / Ca
 3- at e.p, pH of salt of weak acid and strong base;
pH = ½ (pKw + pKa – pCs )
 4-after e.p, pH of strong base;
pH = 14 – pCb
 The suitable indicator used is ph.ph (pH range 8.3 -10)
 M.O indicator is not suitable.
Titration curve of weak base against strong acid
e.g. NH4OH against HCl NH4OH + HCl → NH4Cl + H2O

 1- At beginning, pH of weak base;

pH = pKw – ½ pKb – ½ pCb
 2- During titration, pH of basic buffer;
pH = pkw – pKb + log Cb / Cs
 3- At e.p, pH of salt of strong acid and weak base;
pH = ½ (pKw – pKb + pCs )
 4- After e.p, pH of strong acid;
pH = pCa
 So that, M.O or M.R are used.
 ph.ph is not useful.
 Titration curves of weak acid against weak base and
weak base against weak acid

e.g. NH4OH against CH3COOH

&/or CH3COOH against NH4OH

 Titration curves in both cases are smooth and change of pH

at e.p. is very small.
 So such titrations must be avoided.