Analytical Chemistry (Qualitative and Quantitative Chemistry)

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ACID – BASE EQUILIBRIA, ACID – BASE TITRATIONS

AQUEOUS SOLUTION EQUILIBRIA

 Electrolytes: Substances which form ion in solution
 Strong: Mostly in ionic form in solution
 HCl, HNO3, NaOH, KOH
 HCl + H2O  H+(aq) + Cl-(aq)
 Weak: Mostly not in ionic form in solution
 H2CO3, acetic acid CH3COOH, NH3
 NH3 + H2O NH4+(aq) + OH-(aq)
 Acid – Base Theories:
 Arrhenius Theory (Nobel Prize 1894)
 Acid: any substance that ionizes in water to give hydrogen ions (H+) that associate with the solvent to increase H3O+ in solution.
 Base: ionizes in water to give hydroxyl ions (OH –)
 BrØnsted – Lowry Theory
 Acid = proton donor
 Base = proton acceptor
 Acid base acid base
 HCl + H2O  H3O+  +  Cl-
 (strong) (weak)

 H2CO3 + H2O  H3O+ + HCO3-

 (weak) (strong)

 BrØnsted – Lowry Acid- Base Reactions

 HA   + H2O  H3O+ + A-
acid1 base2 conj. acid2 conj.base1
 base2 + proton  conj. Acid2
 acid1  conj. base1 + proton

 Note: water can act as an acid or a base.

 “amphiprotic” solvent. 

 A Brønsted acid is a proton donor.

 A Brønsted base is a proton acceptor
 Acid = H+
 These are conjugate pairs.
 There must be a proton acceptor before the acid  A “strong” electrolyte is completely dissociated.
releases its proton.  A “week” electrolyte is partially dissociated.

 Other amphiprotic solvents:

 methanol, ethanol, glacial acetic acid

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 CH3OH     CH3CH2OH CH3COOH

 Some amphiprotic solutes:
 HCO3-  + H2O  H3O+ + CO32-
 HCO3-  + H2O  H2CO3 + OH-
 HPO42- + H2O  H3O+ + PO43-
 HPO42- + H2O  H2PO4- + OH-
 Amphiprotic solvent self-ionization
 Autoprotolysis:
 Generic: SH  + SH SH2+ + S-
 Water: H2O + H2O  H3O+ + OH-
 Methanol:  
CH3OH + CH3OH  CH3OH2+ + CH3O-
 Glacial acid acid:
CH3COOH + CH3COOH  CH3COOH2+  + CH3COO-

ACID – BASE EQUILIBRIA IN WATER

 Reaction: HOAc + HOH  H3O+ + OAc-
 Thermodynamic Equilibrium Constant 
 Thermodynamic acidity constant, Koa
 Koa = a(H3O+) . a(OAc-) /a(HOAc) . a(H2O) 
 Thermodynamic autoprotolysis or self-ionization constant
 H2O + H2O  H3O+ + OH-
 Koa = a(H3O+) . a(OH-) /a(HOH) . a(HOH)
 Koa = a(H3O+) . a(OH-)
 Reaction: HOAc + HOH  H3O+ + OAc
 Thermodynamic Equilibrium Constant 
 Thermodynamic acidity constant, Koa
 Koa = a(H3O+) . a(OAc-) /a(HOAc) . a(H2O) 
 Molar equilibrium constants, Ka
 Koa = Ka (ƒ(Η3Ο+)ƒ(ΟAc-) /ƒ(ΗΟΑc))
 Ka = [H3O+][OAc-]/[HOAc]

The pH Scale
 pH = -log a(H+) or pH ≅ -log[H+]
 pAnything = - log Anything
 pKw = -logKw  at 25oC  pKw = 14.00
 Kw = [H+][OH-]
 pKw = pH + pOH =14

Titration is a tried-and-true technique, capable of high precision and accuracy.

VOLUMETRIC ANALYSIS ACID – BASE TITRATIONS

 Titration Curves for Strong Acids and Bases
- Consider acids & bases completely dissociated in HOH
- (e.g.) HCl, HClO4, NaOH, KOH
- Consider only one equilibrium, Kw = [H3O+][OH-]
- Know the stoichiometry of the acid-base reaction
- (e.g.) HCl + NaOH  HOH + Na+ Cl- S.R. =1:1
 What is the pH before a titration begins?
100.0 ml of 0.1000M HCl
= [H3O+] = 1.000 x 10-1M [OH-] = Kw/[H3O+] = 1.000 x 10-13 
o pH = - Log [H3O+] = 1.000 (4s.f.)
pOH = 13.000 (4s.f.)
 How do we find the pH of a titration before the equivalence point is reached?

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When 1.00 mL of 0.1000M NaOH to 100.0mL of 0.1000M  HCl

= [H3O+] = ((CaVa – CbVb) x SR)/(Va + Vb)
= [H3O+] = (100.0mL x 0.1000M – 1.0mL x 0.1000M)x SR)/(101mL)
= [H3O+] = 0.09802M pH = 1.0087 (4s.f.)
= [OH-] = Kw/[H3O+] = 1.020 x 10-13M
= pH = 12.9913 (4s.f.)

 How do we find pH at equivalence point?

 HCl + NaOH HOH + Na+ Cl-
 Autodissociation of water governs the pH at equivalence point.
 HOH + HOH H3O+ + OH-    
Kw = [H3O+][OH-] = 10-14
= c =(Kw)1/2 = 1.000 x 10-7
= pH = 7.0000 (4s.f.)
 How do we find pH after equivalence point?
o Excess base add
[OH-] = ((CbVb – CaVa) x SR)/(Vb + Va)
[H3O+] = Kw /[OH-] pH =-Log [H3O+] 
pOH = -Log [OH-] then pH = 14 - pOH

A strong acid – strong base titration curve has a large end As the concentrations of acid and titrant decrease, the end
point break. point break decreases.
Phenolphthalein is used as an indicator because the So the selection of indicator becomes more critical.
colorless to pink transition is easy to see.

This titration curve was constructed using a spreadsheet

(nextslide).

 Fig. 8.2. Dependence of the magnitude of end-point bread on concentration.

 The concentrations of acid and titrant are the same.

 Fig. 8.1. Titration curve for 100 mL of 0.1 M HCl versus
0.1 M NaOH.

 add standard HCL solution to NaOH solution:
HCl + HOH  H3O+ + Cl-  [H3O+] = C(HCl = Ca
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 NaOH  Na+ + OH-  [OH-] = C(NaOH) = Cb

 HCl + NaOH  Na+ + Cl- + HOH
 H3O+ + OH- HOH net ionic reaction
 When add 1.00 mL of 0.1000M HCl to 100 mL of 0.1000M NaOH (pH = 13.0000)

 What is the pH before titration begins?

100.0 mL of 0.1000M NaOH
= [OH-] = 1.000 x 10-1M  [H3O+] = Kw/[OH-] = 1.000 x 10-13 
= pH = - Log [H3O+] = 13.0000 (4s.f.)

 How do we find the pH of a titration before the equivalence point is reached?

When add 1.00 mL of 0.1000M HCl to 100.0mL of 0.1000M NaOH
= [OH-] = ((CbVb – CaVa) x SR)/(Vb + Va)
= [OH-] = (100.0mL x 0.1000M – 1.0mL x 0.1000M)x SR)/(101mL)
= [OH-] = 0.09802M
= [H3O+] = Kw/[OH-] = 1.020 x 10-13M
pH = 12.9913 (4s.f.)

 How do we find pH at equivalence point?

- HCl + NaOH  HOH + Na+ Cl-
- Autodissociation of water governs the pH at equivalence point
- HOH + HOH  H3O+ + OH-     Kw = [H3O+][OH-] = 10-14
- c =(Kw)1/2 = 1.000 x 10-7 pH = 7.0000 (4s.f.)

 How do we find pH after equivalence point?

- Excess acid added
- H3O+] = ((CaVa – CbVb) x SR)/(Va + Vb)
- pH =-Log [H3O+] 
- pOH = 14 – pH

This is the mirror image of the HCl titration

curve.

Fig. 8.3. Titration curve for 100 mL of 0.1 M NaOH versus 0.1 M HCl.

VOLUMETRIC ANALYSIS ACID – BASE TITRATIONS

 Acid-Base Color Indicators
- Organic weak acids or bases
- Strongly colored acid and/or conjugate base form(*)
- Distinct color change from acid to base form
Acid conj. Base
HIn + OH-  In- + HOH
Color A Color B

- (*) Only very small amount HIn required to give color (<< 10-3 M)
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- Assume presence of HIn does not affect pH of acids/bases > 10-3 M

- Color A Color B
- HIn + HOH  In-  + H3O+    Ka = [H3O+][In]/[HIn]
- [H3O+] = Kax [HIn]/[In-]
 NOTE:
- [HIn]/[In-] determines solution color
- [H3O+] determines [HIn]/[In-] 
- High [HIn]/[In-] (>10:1) gives Color A
- Low [HIn]/[In-] (<1:10) gives Color B

 At what pH does an indicator change color?

- Color A Color B
- HIn + HOH  In-  + H3O+       Ka = [H3O+][In-]/[HIn]
- [H3O+] = Kax [HIn]/[In-]
- pH = pKa + Log([In-]/[HIn])
- Color A, [In-]/[HIn] < 1:10  pH < pKa + Log(1/10)
- Color A, pH = pKa – 1
- Color B, [In-]/[HIn] > 10:1 pH > pKa + Log(10/1)
- Color B, pH = pKa + 1
- Indicator color change occurs at pH = pKa +/− (1) 

pH transition range = pKa ± 1.

We select an indicator with a pKa near the

equivalence point pH.

 For a weak acid, we start with ionization of HA.

 Fig. 8.4. pH transition ranges and colors of some common
 indicators. 
In the buffer region, use the Henderson-Hasselbalch equation.
 -
At the equivalence point, A hydrolyzes as a weak base.
 Beyond the equivalence point, excess OH- dominates.
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 A weak base is treated similarly, but beginning with base and ending with acid. 


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ACID – BASE BUFFERS

BUFFER REGION OF TITRATION CURVES

 Titrating 50.0mL 0.1000M HOAc with 0.1000M

NaOH:
- HOAc + NaOH  HOH + OAc- + Na+
 Buffer Region (e.g. 25.0mL NaOH added):
-
- [OAc ] = Cs = CbVb/(Va+Vb); Ca = (CHAVa-
CbVb)/(Va+Vb)
- Cs= (0.1M) (25.0mL)/(75.0mL) = 0.0333M;
Ca = 0.0333M
 [H3O+] = Ka[HOAc]/[OAc-] = KaCa/Cs
- [H3O+] = (1.75 x 10-5)(0.0333/0.0333) = 1.75 x
10-5 M
- pH = - Log[H3O+] = 4.757 (3s.f.)
 Note: at 50% titration, ½ neutralization
point, pH = pKa
GENERAL RELATIONSHIPS

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 Buffer solution from a week acid and conjugate base:

- A  +  HOH    H3O+  +  A-
- Prepare solution of HA, NaA at CHA, CNaA
- For Ka < 10-3, [HA] ≅ CHA ;  [A-] ≅ c
- [H3O+] = Ka[HA]/ [A-] = Ka CHA/ CNaA

 Henderson – Hasselbalch Equation

- pH = pKa + Log(CNaA/ CHA)

When the Henderson – Hasslebalch (H – H) Equation fails

- Calculating buffer pH when CHA < > [HA]; CNaA < > [A-]:
- (1) HA + HOH  H3O+ + A- 
- (2) A-  +  HOH  HA + OH-
o From Equations (1) and (2):
- (3) [HA] = CHA + [OH-] – [H3O+]
- (4) [A-] = CNaA – [OH-] + [H3O-]
- If [OH-] or [H3O-] can be neglected, use the rigorous form of the buffer equation:
- (5) pH = pKa + Log ([A-]/ [HA])
o Estimate [H3O-] & [OH-] using H-H Equation, and Kw.
o Substitute into equations (3), (4); then use equation (5)

Example Problem
 Add 25.0mL 0.100M NaOH to 50.0mL 0.100M HNO2
- Ka = 7.10 x 10-4; pKa = 3.149 (3s.f.)
- CNaA = (25.0mL)(0.100M)/(75.0mL) = 0.0333M
- CHA  = (50.0mL-25.0mL)(0.100M)/(75.0mL) = 0.0333M
 From H-H Eqn: pH = pKa + Log ((0.0333)/(0.0333) = 3.149
- [H3O+] = 7.10 x 10-4M ; [OH-] = 1.41 x 10-11M
 Considering deviations from H-H assumptions:
- [HA] = CHA + [OH-] – [H3O+] = 0.0325M
- [A-] =  CNaA + [H3O+] – [OH-] = 0.0340M
- pH = pKa + Log([A-]/ [HA]) = 3.149 + 0.0196 = 3.168

Properties of Buffers
 H-H Equation:
- pH = pKa + Log (CNaA/CHA)
- For CNaA = CHA,  pH = pKa
- For added H3O+ or OH- , pH changes slowly
- (e.g. Ka = 10-5 ; CNaA = CHA = 0.1M; pH = 5.0
- Add 0.01M NaOH OH- + HA  HOH + A-
- CNaA = 0.1M + 0.01M = 0.11; CHA = 0.10M – 0.01M = 0.09M 
- pH = pKa + Log ((0.11M)/(0.09M)) = 5.0+0.09 = 5.1

 Buffer Capacity = # moles of strong acid or strong base needed to change pH of 1 L of buffer by 1 pH units

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- (e.g., Ka = 10-5; CHA = CNaA = 0.020M; pH = 5.0

- Add NaOH.  OH- +  HA  HOH + A- 
(C-x) (x) (C+x)
- Log ((0.020 + x)/(0.020 – x)) = new pH – pKa = 1.0
- ((0.020 + x)/(0.020 – x)) = 10; 
- x = 0.016 moles/L = buffer cap.
- For initial buffer concentration = 1.0 M, buffer cap. = 0.82

General Relationships
 Buffer solution from a weak base & conj. acid:
- B + HOH  BH+ + OH-
- Prepare solution of B, BH+ at Cb , Ca
- [OH-] = Kb x Cb/Ca
- pOH = pKb + Log (Ca/Cb)
- pH = 14 – pOH
- (e.g., 0.10M NH3 ; 0.20M NH4Cl ;  Kb = 1.8 x 10-5
 pOH = 4.74 + log((0.20M/(0.10M)) = 5.04; pH = 8.96

Preparation of Buffers
 Use H-H Equation to estimate conditions for desired pH
 Large buffer capacity requires high concentrations
 High ionic strengths
 Activity coefficients less than one
 Use pH meter to determine actual pH 
- ( pH electrode measures H3O+ activity)
 Make final adjustments with acid or conjugate base to achieve desired pH

The weaker the acid, the smaller the break and the
more alkaline the equivalence point.  
Visual indicators can be used for Ka of 10-6.  
A pH meter provides better precision for weaker acids. 

Fig. 8.7. Titration curves for 100 mL 0.1 M weak  acids of different Ka values versus
0.1 M NaOH.  8
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This is the reverse of the HOAc titration curve.

We start with NH3 weak base.  Then we have a buffer mixture
of NH4+ and NH3.
At the equivalence point, we have NH4+,    a weak acid.
Beyond the e.p., we have excess HCl, which suppresses the
hydrolysis of NH4+, and the curve follows that for a strong
base titration. 

Fig. 8.8. Titration curve for 100 mL 0.1 M NH3 versus 0.1 M HCl. 
Fig. 8.9. Titration curves for 100 mL 0.1 M weak bases of different Kb values versus 0.1 M HCl. 

POLYFUNCTIONAL ACID / BASE EQUILIBRIA

The weaker the base, the smaller the break and more acid
the equivalence point.

Visual indicators can be used for Kb of 10-6.  

A pH meter provides better precision for weaker bases. 

 Polyfunctional Acids:
- H3PO4 , H2CO3 , H2SO4 , H2SO3 , H2C2O4 , H2S
- H2S + HOH  H3O+ + HS- Ka1 = 5.7 x 10-8
- HS- + HOH  H3O+ + S2-  Ka2 = 1.2 x 10-15
 Polyfunctional Bases:
- ethylenediamine (NH2C2H4NH2), CO32-, PO43-, HPO42-, S2-
- PO43- + HOH  HPO42- + OH-  Kb1 = Kw/Ka3 = 2.4 x 10-2
- HPO42- +HOH  H2PO4- + OH- Kb2 = Kw/Ka2 = 1.6 x 10-7
POLYFUNCTIONAL ACIDS / BASE TITRATION CURVES
 Polyfunctional acids titrated with strong base:
o Separate equivalence points observed if ratios of successive dissociation constants > ~10-4

o Equivalence point can be observed for dissociation step where Ka > ~10-8
o e.g. H3PO4
o Ka1 = 7 x 10-3, Ka2 = 6 x 10-8, Ka3 = 4 x 10-13

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- First two end points can be observed

- Third end point is not observed
o [H3O+] in solution of amphiprotic anion (HA-)
o OH- + H2A  HA- + HOH
o At first equivalence point, [HA-] = Cs ≅ added OH-
o [H3O+] = ((Ka2Cs + Kw)/(1+ Cs/Ka1))1/2
o If Cs/Ka1 >> 1; Ka2Cs >> Kw; then [H3O+] ≅ (Κa1Ka2)1/2
o Or pH = (pKa1 + pKa2)/2

We start with CO32-, a quite strong base.  Then we have a HCO3-/CO32- buffer.
At the first equivalence point, we have HCO3- ([H+] = √Ka1Ka2).
Then we have a HCO3-/H2CO3  buffer, and H2CO3 at the second equivalence point. 
The first e.p. is used to approximate the second, which is more accurately used. 

Fig. 8.10. Titration curve for 50 mL 0.1 M Na2CO3 versus 0.1 M HCl.
Dashed line represents a boiled solution with CO2 removed. 

Titrate till the methyl red indicator (gradually) changes from yellow through orange
to red (occurs just before the equivalence point).   

Then boil to remove CO2 and continue titration for a sharp end point to a pink
color. 

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We start with a weak acid, H2A, followed by a buffer

region of HA- and H2A.

The first equivalence point is HA- ([H+] ≈ constant).

Then we have a A2-/HA- buffer region, and A2- (a

fairly strong base) at the second equivalence point,
followed by excess titrant. 

Fig. 8.10. Titration curve for 50 mL 0.1 M Na2CO3 versus 0.1 M HCl.
Dashed line represents a boiled solution with CO2 removed. 

Titrate till the methyl red indicator (gradually)

changes from yellow through orange to red (occurs
just before the equivalence point).  
We start with ionization of H2A, a weak to
moderately strong acid. Then boil to remove CO2 and continue titration for
a sharp end point to a pink color. 
In the two buffer regions, use the Henderson-
Hasselbalch equation.

At the first equivalence point, HA- has [H+] ≈

√Ka1Ka2.

At the second equivalence point, A2- hydrolyzes as 11

Fig. 8.11. Titration of 50 mL 0.1 M Na2CO3 with 
a fairly strong base.
0.1 M HCl using methyl red indicator. 
Then excess OH- dominates. 
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Fig. 8.12. Titration of diprotic acid, H2A, with

sodium hydroxide.
Examples with Polyfunctional Acids/Bases
 Example I. Add HCl to Na2CO3 solution.
- (assume concentration = activity)
o Given: for H2CO3 pKa1 = 6.35; pKa2 = 10.33
o Start with: C(HCl) = 0.200M and C(CO32-) = 0.200M
o Desired: pH = 11.00; Cb + Ca = 0.100M; 1.0 L solution
o Use H-H Equation: pH = pKa2 + log (Cb/Ca)
o To get pH = 11; select base = CO32-;  acid = HCO3-
o Because pKa2 = 10.33 (nearest 11.00)
o 11.00 – 10.33 = 0.67 = log(Cb/Ca)
o Cb/Ca = 4.68; Cb + Ca = 0.100M
o Thus, Ca = 0.100M/5.68 = 0.0176M HCO3- ;  Cb = 0.0824M CO32-
o CO32-  + HCl HCO3- + Cl-
o Ca = C(HCl) * V(HCl)/1000mL = 0.0176M
o V(HCl) = 0.0176M*1000mL/0.200M = 88.0mL
o Cb = (C(CO32-) * Vb - C(HCl) * V(HCl))/1000mL = 0.0824M
o Vb = (0.0824 *1000 + 0.200*88.0)/0.200= 500.0mL

 Example II. Add NaOH (b) to H3PO4(a) solution

- (assume concentration = activity)
o Given: for H3PO4, pKa1,2,3 = 2.15; 7.20; 12.35
o Start with: Cb = 0.400M and Ca = 0.400M
o Desired: 1L of pH 7.00; use 200.0 mL acid.
o Procedure: Titrate 200.0mL of H3PO4 w/ NaOH
o Dilute to 1000. mL
o Use H-H Equation: pH = pKa + log(Cb/Ca)
o To get pH= 7.00, select base(b) = HPO42-; acid(a) = H2PO4-
o Because pKa2 = 7.20 (nearest 7.00)
o 7.00-7.20 = - 0.20 = log(Cb/Ca) Cb/Ca = 0.631 
o Because total moles of phosphate remain constant:
 Cb + Ca = Va* Ca/1000mL
 Cb + Ca = (200.0mL)*(0.400M)/1000mL = 0.0800M
 Thus, Cb = 0.631Ca
 Ca + 0.631Ca = 0.0800M;
 Ca = 0.0800M/0.631 = 0.0490 M (in 1L)
 Cb = 0.631* Ca = 0.0310M (in 1L)
o Titration Reaction (to produce HPO42-):
 H3PO4 + NaOH  H2PO4- + HOH + Na+ (1)
 H2PO4- + NaOH  HPO42- + HOH + Na+ (2)
 Va * Ca = # mmoles H2PO4- produced by Rxn (1)
 1000mL * Cb = #mmoles HPO42- produced by Rxn (2)
 Vb * Cb = Va * Ca + Cb * 1000mL
 Vb = (200.0mL)*(0.400M)+(0.310M)*1000mL/(0.400M)
 Vb = 277.5 mL NaOH
 Add 277.5mL NaOH to 200.0mL H3PO4; 

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 dilute to 1000m
The strong acid titrates first.                                                  
At its equivalence point, we have a mixture of NaCl and HOAc,
and the pH is acidic.  

This is followed by a buffer region of OAc- and HOAc, and then

the HOAc equivalence point, where we have OAc-, a weak base.

The weak acid Ka must be no larger than 10-5 to give a sharp

second end point.
For two weak acids, the Ka’s should differ by 104 or more. 

Fig. 8.13. Titration curve for 50 mL of mixture of

  0.1 M HCl and 0.2 M HOAc with 0.2 M NaOH. 

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