Acid-base titrations quantitatively

HClO(aq) + OH-(aq) ClO-(aq) + H2O(aq)

aClO − × aH O + [base] × aH O +
Ka = 3
≈ 3

[acid ] a HClO [ acid ]

= [base] K a × [acid ] [acid ]
⇒ aH + ≈ ⇒ pH ≈ pK a − log
3O
[base] [base]
Henderson-Hasselbalch equation

pH ≈ pK a weak base + strong acid

Determination of
the pKa of an acid
Nils Walter: Chem 260
 Buffers and indicators
Indicators:

[acid ]
log = pH − pK In
acid buffer: stabilizes pH @ [base]
below pH 7 (around pKa) Nils Walter: Chem 260
 Solubility equilibria
Ca(OH)2(s) Ca2+(aq) + 2 OH-(aq)

solubility constant K s = aCa 2+ × aOH −

2

2+ −
molar solubility S = [Ca ] = 1 [ OH ]
2
1 1 (ignoring
⇒ K s = S × (2S ) = 4S ⇒ S ≈ ( Ks )
2 3 3
4 ion-ion interactions;
AgCl(s) Ag+(aq) + Cl-(aq) a ≈ [ ])

K s = a Ag + × aCl − ≈ [ Ag + ][Cl − ] = 1.6 × 10 −10 M 2

AgCl can be precipitated by
+ Ks
S = [ Ag ] ≈ addition of Cl- as a common
[Cl − ] ion from, e.g., NaCl (Le
Chatelier!)
Nils Walter: Chem 260
 Chemistry involving ions: Electrochemistry
Atkins, Chapter 9

Ions migrate in electric fields

-
+ + -
⇓
a current flows
resistivity
potential difference
V ρl
length of sample
molar conductivity:
resistance R = = [Ω] κ
I
current
A cross-sectional area Λm = [ Sm 2 mol −1 ]
c
1
conductivity κ = [Ω −1m −1 = Sm −1 ]
ρ
Nils Walter: Chem 260
siemens
 Ionic conductivities
The molar conductivity varies with concentration
(ions influence each other)
For a strong electrolyte (complete dissociation) [Kohlrausch (1876)]:

Λm = Λm − K c
o Constant to take ion-ion
interactions into account
Limiting molar conductivity (c → 0 M)

Λ m = λ+ + λ −
o

ionic conductivities = contributions

of cation and anion species

Nils Walter: Chem 260