Chapter 8
Activity and Systematic
Treatment of Equilibrium
Objectives
Section 8-1 The Effect of Ionic Strength on Solubility of Salts
Section 8-2 Activity Coefficients
Section 8-3 pH Revisited
Section 8-4 Systematic Treatment of Equilibrium
Section 8-5 Applying the Systematic Treatment of Equilibrium
8: Activities
• Remember equilibrium constant for a reaction is in the
form: [Fe(SCN) 2+ ]
K=
[Fe3+ ][SCN − ]
• The concentration quotient decreases if you add “inert” salt
to the solution
• That is, the equilibrium “constant” is not
really constant
• Concentrations are replaced by activities in
the equilibrium constant
8-1: Effect of Ionic Strength on Solubility
• Look at the following saturated solution in water…
• An interesting effect is observed when an inert salt such
as KNO3 is added to the solution
• Neither K+ or NO3- react with Ca+2 or SO4-2 (means inert)
• When KNO3 added to the saturated solution, more solid
dissolves until the ion concentrations increase therefore
increasing the solubility
8-1: Effect of Ionic Strength on Solubility
• The Explanation
• Consider one Ca+2 ion and one SO4-2 ion in solution
• The ion is surrounded by H2O, cations (K+ and Ca+2), and by
anions (NO3- and SO4-2)
• An anion will be surrounded by more cations than anions
• An cation will be surrounded by more anions than cations
• Ionic atmosphere
• Where these interactions create a region of net positive
charge around any particular anion and a net negative
charge around a cation
• Ions continually diffuse into and out of the ionic
atmosphere and the charge is less than the center anion
or cation
8-1: Effect of Ionic Strength on Solubility
• The Explanation
• The atmosphere attenuates the attraction between the ions
• The net attraction between the cation with its ionic atmosphere and
the anion with its ionic atmosphere is smaller than between pure
cation and anion
• The greater the ionic strength of a solution, the higher the
charge in the ionic atmosphere
• There is less attraction between any particular cation and anion
which increases the solubility
8-1: Effect of Ionic Strength on Solubility
• The Explanation
• The type of inert salt will effect
the ionic strength and the
solubility
• Ionic Strength, μ
• A measure of the total
concentration of ions in solution
• The more highly charged an 1 1
μ = (c1 z1 + c2 z2 + c3 z3 + L ) = ci zi2
2 2 2
ion, the more it is counted 2 2
8-1: Effect of Ionic Strength on Solubility
• The Explanation
• Electrolytes Electrolyte Molarity Ionic strength
• Both the cation and the
anion have a charge of 1 in 1: 1 M M
a 1:1 electrolyte 2: 1 M 3M
• The higher the 3: 1 M 6M
concentration and the 2: 2 M 4M
higher the ionic charge, the
more the ion pairing
8-2: Activity Coefficients
• To account for the effect of ionic strength,
concentrations are replaced by activities, A
• The activity of species C is its concentration multiplied by its
activity coefficient
• The activity coefficient, ɣ, measures the deviation of behavior from
ideality
• Activity is a dimensionless quantity – remember [C] is really [C]/1M
8-2: Activity Coefficients
• The correct form of the equilibrium constant is
• Example: CaSO4 ( s ) 2+ 2−
Ca (aq ) + SO (aq )
4 K sp = 2.4×10 −5
• If a second salt is added to increase ionic strength, the
concentrations of Ca+2 and SO4-2 increase and the activity
coefficients must decrease
8-2: Activity Coefficients
• Activity Coefficients of Ions
• Extended Debye-Hückel equation relates activity coefficients
to ionic strength −0.51z μ
2
log γ =
1 + α μ / 305
• Where is activity coefficient, * is ionic strength, z is ion charge,
and * is ion size (in picometers)
*Refer to Table 8-1 for known
8-2: Activity Coefficients
• Effects of all the things!
• As ionic strength increases, activity coefficient decreases
• Activity coefficient () approaches unity as ionic strength ()
approaches 0
• As magnitude of the charge (z) of the ion increases, activity
coefficient () deviates from unity
• Activity corrections are more important for ions with charge of 3
than charge of 1
• The smaller the ion size (), the more important activity
effects
8-2: Activity Coefficients
8-2: Activity Coefficients
• Interpolation
• The estimation of a number that lies between two values in a
table
• Extrapolation
• Estimating a number that lies beyond values in a table
8-2: Activity Coefficients
• Nonionic Compounds
• Neutral molecules have no ionic atmosphere because they
have no charge
1 (when < 0.1 M)
• Activity concentration for neutral species
• Gases have an activity coefficient 1 (when pressure < 1
bar)
Activity pressure of the gas
8-2: Activity Coefficients
• Above an ionic strength of ~1M, activity coefficients of
most ions increase
• Activity coefficients in concentrated salt solutions are not the same as
those in dilute aqueous solution
• At high ionic strength, γ increases with increasing μ
8-3: pH Again
• pH formula with activity coefficients is more accurate
• When a pH meter is used to measure pH, the negative
logarithm of hydrogen ion activity is measured, not
concentration
• Example:
• pH of pure water is 7.00 ([H+] = 1 × 10−7 M)
• pH of wated in the presence of salt is 6.98 ([H+] = 1.26 × 10−7 M)
because of the effect on the H+ and OH- activities
• This may seem like a small difference but this corresponds to a
concentration change of 26% [H+]
8-4: Systematic Treatment of Equilibrium
• A way to deal with all types of chemical equilibria,
regardless of their complexity
• Set up general equations.
• Introduce specific conditions and/or reasonable approximations
• Key is to write as many independent algebraic equations
as there are unknown species in the system
• Chemical equilibrium
• Charge balance (only 1)
• Mass balance (multiple)
8-4: Systematic Treatment of Equilibrium
• Charge Balances
• An algebraic statement of electroneutrality
• The sum of the positive charges in solution equals the sum of the
negative charges in solution
• The general form of the charge balance for any solution is
• Where C is the concentration of a cation, n is the charge of the
cation, A is the concentration of an anion, and m is the magnitude
of the charge of the anion
8-4: Systematic Treatment of Equilibrium
• Charge Balances
• Example:
8-4: Systematic Treatment of Equilibrium
• Mass Balances
• A statement of the conservation of matter
• The quantity of all species in a solution containing a
particular atom (or group of atoms) must equal the amount
of that atom (or group) delivered to the solution
Formal concentration = all relevant species after reaching equilibrium
i
8-4: Systematic Treatment of Equilibrium
• Mass Balances
• Example:
• The mass balance states that the quantity of dissociated and
undissociated acetic acid in the solution must equal the amount of
acetic acid put into the solution
• Activity coefficients do not appear in the mass balance
• The concentration of each species counts exactly the number of
atoms of that species
8-4: Systematic Treatment of Equilibrium
• Mass Balances
• Example:
• Know that there must be three iodate ions for each lanthanum ion
dissolved and therefore the mass balance is
[IO −3 ] = 3[La 3+ ]
8-4: Systematic Treatment of Equilibrium
• Summary
• Write the pertinent reactions (balanced chemical reactions)
• Write the charge balance equation
• Write mass balance equations (may be more than one)
• Write the equilibrium constant expression for each chemical
reaction
• This step is the only one in which activity coefficients appear
• Count the equations and unknowns
• There should be as many equations as unknowns
• If not, you must either find more equilibria or fix some concentrations at
known values
• Solve for all unknowns
8-5: Application of Systematic Treatment
• Example
• Find the concentrations of species in an aqueous solution
containing 0.0100 mol NH3 in 1.000L
• Step 1: Pertinent Reactions
• Primary equilibrium
NH 3 + H 2 O NH +4 + OH − K b = 1.76 10−5
• Second equilibrium in every aqueous solution
H 2O H + + OH − K W = 1.00 10−14
8-5: Application of Systematic Treatment
• Example
• Find the concentrations of species in an aqueous solution
containing 0.0100 mol NH3 in 1.000L
• Step 2: Charge Balance
• The sum of positive charge equals the sum of negative charge
[NH +4 ] + [H + ] = [OH − ]
• Step 3: Mass Balance
• All of the ammonia delivered to the solution is either in the form
NH3 or NH4+
• These two must add up to 0.0100M
+
[NH3 ] + [NH ] = 0.010 0 M F
4
8-5: Application of Systematic Treatment
• Example
• Find the concentrations of species in an aqueous solution
containing 0.0100 mol NH3 in 1.000L
• Step 4: Equilibrium Expressions
• This is the only step in which activity coefficients enter the problem
[NH +4 ] NH+ [OH − ] OH−
Kb = 4
[NH 3 ] NH 3
+ −
K W = [H ] H+ [OH ] OH−
8-5: Application of Systematic Treatment
• Example
• Find the concentrations of species in an aqueous solution
containing 0.0100 mol NH3 in 1.000L
• Step 5: Count
4 equations: Kb, Kw, charge balance, mass balance
4 unknowns: [NH3 ], [NH 4 + ], [H + ], [OH − ]
8-5: Application of Systematic Treatment
• Example
• Find the concentrations of species in an aqueous solution
containing 0.0100 mol NH3 in 1.000L
• Step 6: Solve
• Start by ignoring activity coefficients
• Approach is to eliminate one variable at a time until only one unknown is left
• Since acid-base problem, start by expressing as much as possible in terms
of [H+]
− +
• Rearrange Kw [OH ] = K w /[H ]
• Substitute into charge balance [NH +4 ] + [H + ] = [OH − ] solve for NH4+
[NH +4 ] + [H + ] = K w / [H + ]
[NH +4 ] = K w /[H + ] − [H + ]
8-5: Application of Systematic Treatment
• Example
• Find the concentrations of species in an aqueous solution
containing 0.0100 mol NH3 in 1.000L
• Step 6: Solve
• Substitute into mass balance [NH3 ] + [NH +4 ] = 0.010 0 M F solve for NH4+
[NH 3 ] + K w /[H + ] − [H + ] = F
[NH 3 ] = F− K w /[H + ] + [H + ]
• Substitute into Kb
8-5: Application of Systematic Treatment
• Example
• Find the concentrations of species in an aqueous solution
containing 0.0100 mol NH3 in 1.000L
• Step 6: Solve
• Substitute into mass balance [NH3 ] + [NH +4 ] = 0.010 0 M F solve for NH4+
[NH 3 ] + K w /[H + ] − [H + ] = F
[NH 3 ] = F− K w /[H + ] + [H + ]
• Substitute into Kb
Solubility and Hydrolysis of Thallium(I) Azide (1
of 2)
Step 1: pertinent reactions
TIN 3 ( s) Tl+ (aq) + N 3− (aq) K sp = 10−3.66
N 3− + H 2 O NH 3 + OH − K b = 10−9.35
H 2O H + + OH − K w = 10−14.00
Step 2: charge balance
[Tl+ ] + [H + ] = [N 3− ] + [OH − ]
Step 3: mass balance
[Tl+ ] = [N 3− ] + [NH 3 ]
Solubility and Hydrolysis of Thallium(I) Azide (2 of
2)
Step 4: equilibrium expressions
K sp = [Tl+ ] Tl+ [N 3− ] N− = 10−3.66
3
[HN 3 ] HN3 [OH − ] OH−
Kb = = 10−9.35
[N 3− ] N−
3
K w = [H + ] H+ [OH − ] OH− = 10−14.00
Step 5: count
5 equations: Ksp, Kb, Kw, C.B., M.B.
5 unknowns: [Tl+ ], [N 3− ], [HN 3 ], [H + ], [OH − ]
Step 6: solve Use a spreadsheet and ignore activity coefficients.
Number of concentrations to estimate = (number of unknowns) − (number of equilibria)
=5−3=2
Figure 8-9 Thallium(I) Azide Solubility
Spreadsheet
Figure 8-10 Solver Parameters and Solver Options
Figure 8-11 Thallium(I) Azide Solubility
Spreadsheet
Solubility of Magnesium Hydroxide with Activity
Coefficients (1 of 2)
Step 1: pertinent reactions
Mg(OH) 2 ( s) Mg 2+ (aq) + 2 OH − ( aq) K sp = 10−11.15
Mg 2+ + OH − MgOH + K1 = 1 = 102.6
H 2O H + + OH − K w = 10−14.00
Step 2: charge balance
2[Mg 2+ ] + [MgOH + ] + [H + ] = [OH − ]
Step 3: mass balance
2[Mg 2+ ] + [MgOH + ] + [H + ] = [OH − ] (equivalent to charge balance)
Solubility of Magnesium Hydroxide with Activity
Coefficients (2 of 2)
Step 4: equilibrium expressions
K sp = [Mg 2+ ] Mg2+ [OH − ]2 OH
2
− = 10
−11.15
[MgOH + ] MgOH+
K1 = = 102.6
[Mg 2+ ] Mg2+ [OH − ] OH−
K w = [H + ] H+ [H − ] OH− = 10−14.00
Step 5: count
4 equations: Ksp, K1, Kw, C.B./M.B.
4 unknowns: [Mg 2+ ], [Mg OH + ], [H + ], [OH − ]
Step 6: solve Use a spreadsheet and include activity coefficients.
Number of concentrations to estimate = (number of unknowns) − (number of equilibria)
=4−3=1
Figure 8-12 Magnesium Hydroxide Solubility Spreadsheet