5.

111 Lecture Summary #18 Wednesday, October 22, 2014

Reading for Today: Sections 10.1-10.5, 10.9 (Sections 9.1-9.4 in 4th ed.)
Reading for Lecture #19: Sections 10.9-10.13 (Section 9.4-9.5 in 4th ed.)

Topics: Chemical Equilibrium

I. Nature of Chemical Equilibrium
II. Meaning of K
III. External Effects on K

Chemical reactions reach a state of dynamic equilibrium in which the rates of forward and
reverse reactions are equal and there is no net change in composition.

Consider: N2(g) + 3H2(g) 2NH3(g) ∆G° = -32.90 kJ/mol

Free energy, G
Concentration

Pure Pure
reactants products
time
Progress of reaction

When the reaction mixture has not produced enough products to have reached
equilibrium, the spontaneous direction of change is toward more products
(∆Gforward reaction < 0).

When excess products are present (ex. pure ammonia), the reverse reaction is spontaneous
(∆Gforward reaction > 0).

The reaction free energy (∆G) changes as the proportion of reactants and products
change .

∆G = ∆G° + RT ln Q Where

∆G = reaction free energy at any definite, fixed composition of the reaction mixture.
∆G° = is the difference in free energy of the products and reactants in their standard states.
R = universal gas constant, T = Temperature, and Q = reaction quotient

1
For aA + bB cC + dD

In gaseous phase in solution

(PC/Pref)c (PD/Pref)d ([C]/Cref)c ([D]/Cref)d
∆G = ∆G° + RT ln ∆G = ∆G° + RT ln
(PA/Pref)a (PB/Pref)b ([A]/Cref)a ([B]/Cref)b

Q Q
Pref = 1 bar Cref = 1 M and [C] in M
P x = partial pressure
Q = PCc PDd Q = [C]c [D]d

PAa PBb [A]a [B]b

At equilibrium ∆G = 0 and Q = K (the equilibrium constant),

0 = ∆G° + RT ln K

∆G° = -RT ln K

K = is the equilibrium constant. It has the same form as Q , but only uses the
amounts of products and reactants at equilibrium.

We can rewrite ∆G = ∆G° + RT ln Q as

∆G = -RT ln K + RT ln Q or
∆G = RT ln (Q/K)

Relationship between K and Q:

If Q < K, ∆G is negative and the forward reaction will occur
If Q > K, ∆G is positive and the reverse reaction will occur

Example: N2(g) + 3H2(g) 2NH3(g)

If K=1.9 x 10-4 at 400°C, and PN2 = 5.5 bar PH2=2.2 bar PNH3 = 1.1 bar at 400°C, which
direction will the reaction go?

Q=

2
WHAT DOES K TELL US?

K tells us about the mixture of products and reactants at equilibrium, whether we can
expect high or low concentration of products at equilibrium.

when K > 1, products

when K < 1, products

For K >1
2NO2 (g) N2O4 (g) ∆G° = -4.76 kJ/mol and K = 6.84 at 298 K

Start with 1.000 bar of NO2 (reactant) and no N2O4 (product)

so Q < K and ∆G < 0, and the reaction goes forward
partial pressures

N2O4

NO2

time

Calculate the partial pressures of NO2 and N2O4 at equilibrium using the given value of K
and the given starting concentration of reactant.

2NO2 N 2 O4
initial partial pressure (bar) 1.000 0
change partial pressure +X
equilibrium partial pressure +X

K = 6.84 =

x = _____________bar (_________)

1.000 – 2x = 1.000 – 2(________) = __________bar (__________)

For K >1, more products at equilibrium.

3
Relationship between ∆G° and the magnitude of K:

rewrite ∆G° = -RT ln K as

K = exp [-∆G° / RT] K is large if ∆G° is ???

Consider the decomposition of baking soda at two different temperatures.

2NaHCO3(s) Na2CO3(s) + CO2(g) + H2O(g)

∆G° = +36 kJ/mol at room temperature K =

∆G° = -15 kJ/mol at 350°F K =

At room temperature, very very little CO2 is produced so bread will not rise.

Chemical equilibrium applies to large molecules (like proteins) too.

Chemical Equilibrium: In Her Own Words

Nozomi Ando discusses how

chemical equilibrium relates
to her research on understanding proteins
that are successful chemotherapeutic
targets.

Image from "Behind the Scenes at MIT”. The Drennan Education Laboratory.
Licensed under a Creative Commons Attribution-NonCommercial-ShareAlike License.
Nozomi’s video can be found at http://chemvideos.mit.edu/all-videos/

EXTERNAL EFFECTS ON K

Principle of Le Châtelier: A system in equilibrium that is subjected to stress will react in a

way that tends to the effect of the stress.

Le Châtelier's principle provides a way to predict qualitatively the direction of change of a

system under an external perturbation.

4
ADDING AND REMOVING REAGENTS

N2(g) + 3H2(g) 2NH3(g)

Figure by MIT OpenCourseWare.

1) ADDING MORE REACTANT

If you are at equilibrium and then add more hydrogen, according to Le Châtelier's
principle, the system will tend to minimize the increase in the number of hydrogen
molecules. Reaction shifts to the right toward .

This can be explained in terms of Q and K. When reactants are added, Q falls below K
momentarily, because the reactant concentration term appears in the denominator.

Q = [products]/[reactants] K= {[products]/[reactant]} equilibrium

With Q<K, ΔG is negative, and the system responds by making more products (reaction
proceeds in the forward direction).

2) ADDING MORE PRODUCT

Q rises above K. Q is larger because product term is in numerator (K is unchanged). With

Q>K, ΔG is positive, and the reaction goes toward reactants (reaction proceeds in the
reverse direction).

3) REMOVING PRODUCT
Q K and Δ G is , so the reaction shifts to

5
5.111 Lecture Summary #19 Friday, October 24, 2014

Reading for Today: Sections 10.9-10.13 (Sections 9.9-9.13 in 4th ed.)

Reading for Lecture #20: Sections 9.8 - 9.13 (8.8-8.13 same in 4th ed.) on solubility;
Sections 11.1 – 11.2, 11.4-11.6 (10.1-10.2, 10.4-10.6 in 4th ed.) on acids and bases.

Topics: I. External effects on K (Le Châtelier’s Principle) continued

II. Temperature dependence of K
III. Applications of Le Le Châtelier’s Principle
IV. Sig figs for logs

I. EXTERNAL EFFECTS ON K (LE CHÂTELIER’S PRINCIPLE) CONTINUED

A. CHANGING THE VOLUME OF A GASEOUS SYSTEM

A decrease in the volume of a gaseous system FDXVHVDQLQWKHWRWDO

pressure.

I '($/*$6/$:ZKHUH3LVSUHVVXUH9LV9ROXPe,
T is temSHUDWXUHQLV5LVWKHLGHDOJDVFRQVWDQW

Le Châtelier's principle predicts that the system would respond, if possible, in such a
way as to reduce the total pressure.

Example 2P2 (g) P4 (g)

expand compress

i) A decrease in volume shifts the reaction to the right (toward product).

This change occurs because for every 2 molecules of P2 consumed only 1 molecule of P4 is
formed.

A shift to the right reduces the total pressure, partially compensating for the external
stress of the volume change.

1
Now consider in terms of Q and K.
Suppose the volume is decreased by a factor of 2 at constant temperature.
This change will increase the partial pressure of P2 by 2 and of P4 by 2, initially.
PP
4 2 1
Q = 2
= =
(PP ) 22 2
2
Q decreases by a factor of 2, and Q < K. ∆ *LV

Reaction proceeds in forward direction (toward products) until Q=K again.

ii) An increase in volume shifts the reaction to the left (toward reactants).

For every one molecule of P4 that is consumHGPolecules of P2 are formed.

Thus a shift of the reaction toward reactants, increases the total pressure.

B. ADDING INERT GAS

Case 1) For 2P2 (g) P4, what happens if an inert gas is added to the container
increasing the total pressure at constant temperature?

$QVZHU Why?
Q depends on the partial pressure of P2 and P4 gases and the partial pressures do not
change here.

Review Partial Pressure: The partial pressure is the pressure that each gas would exert if
it alone were present in the container.
1 atm 1 atm 2 atm

O2 N2 mixture of O2 and N2

PA = nA RT

Ptot = P A + PB + P C + etc = (nA + nB + nC + etc) RT = ntot RT

V V

2
When the total pressure increases due to the addition of an inert gas, the partial pressure
of each gas is unchanged. When the partial pressure is the same, Q doesn’t change. When
Q doesn’t change, there is no shift.

Case 2) For 2P2 (g) P4 (g), what happens if an inert gas is added to the container but
the total pressure and temperature are kept constant?

Answer: the reaction

For the pressure to be kept constant, the of the container must have
increased. And when increases, partial pressures decrease, causing
this reaction to .

C. CHANGING THE TEMPERATURE

Raising the temperature of an equilibrium mixture by adding heat causes the reaction to
shift such that some of the heat is absorbed.

Le Châtelier's principle is consistent with this observation.

Raising the temperature of an exothermic reaction favors the formation of .

Heat produced
Reactants Products (exothermic direction)

Heat absorbed
Reactants Products (endothermic direction)

Raising the temperature of an endothermic reaction favors the formation of products.

Heat absorbed
Reactants Products (endothermic direction)

Heat produced
Reactants Products (exothermic direction)

Here ∆H is the predictive tool

Example 2SO2 (g) + O2 2SO3 (g) ∆H° = -197.78 kJ/mol

If heat is added, which direction will the reaction go?

3
II. TEMPERATURE DEPENDENCE OF K

K can change with temperature and reaction rates can change with temperature.

∆G° = -RT ln K = ∆H° - T ∆S° or ln K = -∆H°/RT + ∆S°/R

Since it is reasonable to assume that ∆H° and ∆S° are approximately independent of
temperature over the range of temperatures of interest, K changes with a change in T.

Consider a reaction carried out at Temperatures T1 and T2:

ln K2 = -∆H°/RT2 + ∆S°/R and ln K1 = -∆H°/RT1 + ∆S°/R

Subtracting the second equation from the first gives:

K2 - ∆ H° 1 1
ln = Van't Hoff Equation
-
K1 R T2 T1

K2 - ∆ H° 1 1
ln = Van't Hoff Equation
-
K1 R T2 T1

If ∆H° < 0
T2 > T1 then (-)(-)(-) = (-) K 1 > K2

T2 < T1 then (-)(-)(+) = (+) K 1 < K2

If ∆H° > 0
T2 >T1 then (-)(+)(-) = K1 K2

T2 < T1 then (-)(+)(+) = K1 K2

4
III. APPLICATIONS OF LE CHÂTELIER’S PRINCIPLE

A. MAXIMIZING THE YIELD OF A REACTION

The Harber-Bosch Process.

N2(g) + 3H2(g) 2NH3(g) exothermic reaction

1.6 x 1010 kg of ammonia produced by this process per year in US

low temperature favors products, good but low temperature slows rate, bad
Compromise temperature used is 500°C.

What are other ways to drive the reaction toward products?

All living things need nitrogen, and there is lots of N2 in the air, but it is hard to split N2.
Thus, we use the environmentally unfriendly Harber-Bosch Process, but bacteria can
catalyze the same reaction using an enzyme called nitrogenase.

B. LE CHÂTELIER AND HEMOGLOBIN

The combination of oxygen with hemoglobin (Hb), which carries oxygen through the
blood, can be represented by

Hb (aq) + O2 (aq) HbO2 (aq)

where HbO2 is oxyhemoglobin (oxygen bound to hemoglobin)

At an altitude of 3 km the partial pressure of oxygen is only about 0.14 atm, compared to
0.2 atm at sea level.

According to Le Châtelier's principle, the equilibrium would be shifted to the left. This
change causes hypoxia.

How can the body compensate?

Hb (aq) + O2 (aq) HbO2 (aq)

5
IV. SIG FIG RULES FOR LOGS AND EXPONENTIALS (PAGE A5 IN BOOK)

log (7.310 x 103) = 3.8639 (4 sig figs in mantissa)

log (7.310 x 1023) = 23.8639 (4 sig figs in mantissa)
The characteristic (left of decimal point) is determined solely by the location of the
decimal point in the number and not by the number's precision, it is not included when
counting sig figs. The mantissa (right of decimal point) should be written with as many
sig figs as the original number.

100.389 =2.45 (3 sig figs in answer)

1012.389=2.45 x 1012(3 sig figs in answer)

There are no simple rules for assessing significant figures for natural logarithms. One
should convert ln to log and then use log rules, but for the purposes of this course, just
use log sig fig rules for ln too.

Let’s try an example

6
5.111 Lecture Summary #20 Monday October 27, 2014

Reading for Today: Sections 9.8 - 9.13 (8.8-8.13 same in 4th ed.) on solubility; Sections 11.1
– 11.2, 11.4-11.6 (10.1-10.2, 10.4-10.6 in 4th ed.) on acids and bases.

Reading for Lecture #21: Sections 11.7-11.9, 11.11-11.13 (10.7 -10.9, 10.11 – 10.13 in 4th ed).

Topics: I. Solutions and Solubility

II. Classification of Acids and Bases

I. SOLUTIONS AND SOLUBILITY

So far, we’ve been discussing pure compounds. However, most substances are .

Solutions are homogeneous mixtures.

Solvent: the substance that does the dissolving (i.e. water)
Solute: any dissolved substance in a solution

MOLAR SOLUBILITY
Ionic solids. Consider NaCl dissolving in water.

Polar water molecules ions at the surface of the

salt’s crystal lattice, prying some of the Na+ and Cl- ions away.

Stirring can the process by bringing more free

water molecules to the surface of the solid, and taking more
hydrated ions away.

Solubility equilibrium: NaCl (s) Na+ (aq) + Cl- (aq)

Ksp = [Na+][Cl-] where sp stands for “solubility product”

is a measure of the dissolution of an ionic solid in water.

Note NaCl does not appear in the expression since it is a solid.

Organic solids. Consider glucose dissolving in water.

Water molecules form hydrogen bonds to the glucose molecules near the surface of a
glucose crystal. Some glucose molecules are pulled away by the surrounding water (are
solubilized), other molecules are not.

Glucose is a hydrogen bond .

A solution is when the solvent has dissolved all the solute that it can
and some undissolved solute remains.

The dissolved and undissolved solute are in

with each other.

1
The amount that dissolves depends on the molar solubility (s) of the substance.

Molar solubility (s) of a substance is its molar concentration in a saturated solution, and
represents the limit of its ability to dissolve in a given solvent. (units: )

Note: molar solubility (s) and Ksp are not the same, but they can be calculated from each
other. [Na+] = [Cl-] = s (is the molar solubility of either ion at equilibrium), thus

Ksp = [Na+][Cl-] = s2 for this particular ionic compound.

Like-Dissolves-Like Rule
A polar liquid like water is generally the best solvent for ionic and
compounds.

Conversely, nonpolar liquids, including hexane and tetrachloroethane (used in dry

cleaning), are better for nonpolar (hydrophobic) compounds.

Applications of this rule:

pharmaceutical drug design -- solubility of nonpolar enzyme inhibitors in aqueous
solutions.
cleaning products -- want to dissolve polar and nonpolar stains

IMPACT OF PRESSURE AND TEMPERATURE ON

SOLUBILITY

Pressure and Gas Solubility

Henry’s Law: the solubility of a gas (s) is directly proportional to

its partial pressure (P).

s = kHP where kH is Henry’s constant, and depends on

the gas, the solvent, and the temperature.
© W. H. Freeman & Co Ltd. All rights reserved. This content
is excluded from our Creative Commons license. For more
information, see http://ocw.mit.edu/help/faq-fair-use/.
The solubility of a gas is to its partial pressure, because an increase
in pressure corresponds to an in the rate at which gas molecules
strike the surface of the solvent.
In Their Own Words
Former MIT postdoctoral scholar Dr. Hector Hernandez discusses
how gas solubility and Le Chatelier’s principle relate to his research
on CO2 capture and storage in the lab of MIT Professor Janelle
Thompson.

Hector’s s video can be found at:

http://chemvideos.mit.edu/all-videos/.

Courtesy of Hector Hernandez. Used with permission.

Temperature and Solubility

Most substances dissolve more at higher temperatures, but that
doesn’t necessarily mean that they are more soluble (that is reach a higher final
concentration of solute)

Most gases are soluble in warm water than in cold water.

Solids show a more varied behavior.

ENTHALPY, ENTROPY AND GIBBS FREE ENERGY OF SOLUTIONS

The change in molar enthalpy when a substance dissolves is called the enthalpy of
solution ∆Hsol. The change can be measured calorimetrically from the heat released or
absorbed when the substance dissolves at constant pressure.

A enthalpy of solution tells us that energy is released as heat when a

substance dissolves.

A enthalpy of solution tells us that energy is absorbed as heat when a

substance dissolves.

To predict whether dissolving of a substance is spontaneous at constant pressure and

tem perature, we need to consider .

Since the disorder of a system typically increases when a solid dissolves, we expect the
entropy of the system to *.

If ∆Hsol is negative, and the entropy of the system increases when the solute dissolves,
then we expect the dissolving process to be .

* In some cases, the entropy of the system is lowered when a solution forms because the
solvent molecules form a cage-like structure around the solute molecule.

Here even if ∆Hsol is negative, ∆G might be positive.

This cage-effect is why some hydrocarbons are insoluble

in water even though they have weakly negative
enthalpies of solution.

© W. H. Freeman & Co Ltd. All rights reserved. This content

is excluded from our Creative Commons license. For more
information, see http://ocw.mit.edu/help/faq-fair-use/.

For gases, which enter a condensed state with much less freedom of movement when
they dissolve in a liquid, the entropy of solution is and
solubility as the temperature rises.

What is the effect on the spontaneity of dissolving if ∆Hsol is positive?

3
II) CLASSIFICATION OF ACIDS AND BASES

1. Arrhenius - a narrow definition of acids and bases

An acid is a substance that when dissolved in water increases the concentration of

hydrogen ions.

A base is a substance that increases the hydroxide concentration.

2. Brønsted-Lowry - a broader definition

A Brønsted-Lowry acid - a substance that can a hydrogen ion (H +)

A Brønsted-Lowry base - a substance that can a hydrogen ion (H +)

Example 1

CH3COOH (aq) + H2O (l)

H3O+ (aq) + CH3COO- (aq)
Acid1 Base2 Acid2 Base1

(note: hydronium ion H3O+ (aq) is used instead of H+ (aq) to represent the true nature of

hydrogen ions in water)

Acid-bases occur as conjugate acid-base pairs.

CH3COOH and CH3COO- are a pair. H2O and H3O+ are a pair.

• The conjugate base of an acid is the base that is formed when the acid has donated
a hydrogen ion (proton).
• The conjugate acid of a base is the acid that forms when base accepts a hydrogen
ion (proton).

Example 2 Which are Brønsted-Lowry acids and which are Brønsted-Lowry bases?

(a) HCO3- (aq) + H2O (l) H3O+ (aq) + CO3- (aq)

(b) HCO3- (aq) + H2O (l) H2CO3 (aq) + OH- (aq)

amphoteric - molecules that can function either as acids or bases depending on the
reaction conditions (example H2O).

4
3. Lewis Acid and Base - more general definition - applies to reactions that don't
involve a hydrogen ion

Lewis base - species that lone-pair electrons

Lewis acid - species that such electrons

Example 1

F H F H

F B + N H F B N H

F H F H

Ammonia is the Lewis base. It donates lone-pair electrons to BF3, the Lewis acid and the
electron acceptor.

5
5.111 Lecture Summary #21 Wednesday, October 29, 2014

Reading for Today: Sections 11.7-11.9, 11.11-11.12 (10.7 -10.9, 10.11 – 10.12 in 4th ed.)
Reading for Lecture #22: Sections 11.13, 11.18-11.19, 12.1-12.3 (10.13, 10.18-10.19, 11.1-
11.3 in 4th ed.)

Topics: I. Definitions and Relationships between pKw, pH, and pOH

II. Strengths of Acids and Bases
III. Equilibrium Acid-Base Problems (Weak Acids and Weak Bases)

I. Definitions and Relationships between pKw, pH, and pOH

Autoionization of water and definition of pKw

2H2O (l) H3O+ (aq) + OH- (aq) or H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)
acid base acid base

How much H2O is in a glass of water?

2H2O (l) H3O+ (aq) + OH- (aq) ∆G° = +79.89 kJ/mol

- ( 7.989 x 104 J/mol)

ln K = -∆G°/RT = = -32.24
(8.3145 J/Kmol)(298.0 K)

K= at 298 K

This very value indicates that only a small proportion of water

molecules are ionized. Concentration of ions due to autoionization of water is very low,
about 1 molecule in 200 million.

K = [H3O+][OH-] This K is called Kw.

Because Kw is an equilibrium constant, the product of [H3O+][OH-] is always 1.0 x 10-14

at 298 K.

Note: Because the concentration of the solvent, H2O, does not change significantly in a dilute
solution, it does not enter the equilibrium expression. The solvent, water, is very nearly pure,
and pure liquids and pure solids are not included in equilibrium expressions.

Definitions of pH and pOH

pH Function: pH = -log

pOH Function: pOH = -l og

1
Relationship between pH, pOH and pKw
Kw = [H3O+][OH-] = 1.0 x 10-14 at 25°C
logKw = log[H3O+] + log[OH-]
-logKw = -log[H3O+] - log[OH-]

pKw = + = 14.00 at 25°C

II. Strength of Acids and Bases

pH of pure water pH = -log (1.0 x 10-7) = 7.00

pH of an acid solution is
pH of an base solution is

EPA defines waste as "corrosive" if the pH is lower than 3.0 or higher than 12.5.

Demo: let’s check out the acidity or basicity of common household products.

Acid Strength

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3COO- (aq)

The equilibrium constant for an acid in water is termed Ka (the acid ionization constant)

For this reaction, Ka =

The value for Ka is 1.76 x 10-5 at 25°C. This small value tells us that only a small number
of CH3COOH molecules donate their proton when dissolved in water (weak acid).

Generic expressions for acids in water:

HA (aq) + H2O (l) H3O+ (aq) + A- (aq) ACID (HA) IN WATER

BH+ (aq) + H2O (l) H3O+ (aq) + B (aq) ACID (BH+) IN WATER

A strong acid has a Ka >1 which means that the acid ionizes alm ost .

A weak acid has a Ka <1. The reaction with water does not produce many ionized
species before equilibrium is reached.

2
pKa = -log Ka

The lower the value of Ka, the higher the value of pKa.
The higher the pKa WKHWKHDFLG

A few Ka and pKa values at 25°C

ACID Ka pKa
HI ~1011 ~ -11
HCl ~107 ~ -7
H2SO3 1.54 x 10-2 1.81
HCOOH 1.77 x 10-4 3.75

Base Strength

NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

The equilibrium constant for a base in water is termed Kb (the base ionization constant)

For this reaction, Kb =

Kb is 1.8 x 10-5 at 25°C. This small value tells us that only a small amount of NH3 ionizes
to NH4+ and OH- in solution. A strong base reacts essentially completely to give OH-
(aq) when put in water. NH3 is not a strong base. It is a moderately weak base.

Generic expressions for bases in water:

B (aq) + H2O (l) BH+ (aq) + OH- (aq) BASE (B) IN WATER

A- (aq) + H2O (l) HA (aq) + OH- (aq) BASE (A-) IN WATER

A strong base ionizes almost completely to give OH- in water.

pKb = -log Kb

larger Kb, stronger base

larger pKb EDVH

3
Strength of Conjugate Acids and Bases

The stronger the acid, the

its conjugate base.

The stronger the base, the

its conjugate acid.

Why this relationship? Ka and Kb are

related and so are pKa and pKb.

Ka x Kb = Kw = 1.0 x 10-14

log Ka + log Kb = log Kw or

pKa + pKb = pKw = 14.00

An acid/base and its conjugate base/acid can’t both be strong.

Strong acids and bases push drive the reaction toward complete ionization:

Strong acid HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

Strong base B (aq) + H2O (l) BH+ (aq) + OH- (aq)

Whereas weak acids and bases are in equilibrium with their conjugates bases and acids:

Weak acid HA (aq) + H2O (l) H3O+ (aq) + A- (aq)

Weak base B (aq) + H2O (l) BH+ (aq) + OH- (aq)

III. Equilibrium Acid-Base Problems

1. weak acid in water salt in water
2. weak base in water
3. strong acid in water
4. strong base in water
5. buffer

Equilibrium Involving Weak Acids

Example: Vitamin C (ascorbic acid, HC6H7O6) has a Ka of 8.0 x 10-5. Calculate the pH of
a solution made by dissolving 500. mg in 100. mL of water.

0.500 g x 1 mol/176.126 g = 2.84 x 10-3 mol

2.84 x 10-3 mol/0.100 L = 0.0284 M

4
HC6H7O6 (aq) + H2O (l) H3O+ (aq) + C6H7O6- (aq)

HC6H7O6 H3O+ C6H7O6-

initial molarity 0.0284 0 0
change in molarity -x +x +x
equilibrium molarity

Ka = 8.0 x 10-5 = [H3O+][C6H7O6-] x2

=
[HC6H7O6] 0.0284- x

If x<< 0.0284, then (0.0284-x) ~= 0.0284.

Ka = 8.0 x 10-5 = x2
0.0284

x = 0.00151 (really 2 sf, but carry extra)

Check assumption. Is 0.0284 - 0.00151 ~= 0.0284?

You can use assumption if x is less than 5% of the value in question (This 5% policy
holds for any chemical equilibrium problem, not just acid-base).

Here (0.00151/0.0284) x 100% = 5.3% (more than 5%), so must use the quadratic
equation.

This value is sometimes called the percentage ionized or percentage deprotonated.

Using quadratic eq, x = 0.00147 (really 2 sf)

pH = -log [1.47 x 10-3 ] =

Equilibrium Involving Weak Bases

Example: NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq) Kb is 1.8 x 10-5 at 25°C.

Calculate the pH of a 0.15 M NH3 solution at 25°C.

NH3 (aq) NH4+ (aq) + OH- (aq)

initial molarity 0.15 0 0
change in molarity
equilibrium molarity

5
base
ionization (Kb) = [NH4+][OH-] = Using assumption, x= 0.00164
constant [NH3]

Check assumption:

pOH = -log [OH-] = -log [0.00164] = 2.79

pH =

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5.111 Lecture Summary #22 Wednesday, October 31, 2014

Reading for Today: Sections 11.13, 11.18-11.19, 12.1-12.3 in 5th ed. (10.13, 10.18-10.19, 11.1-11.3
in 4th ed.)
Reading for Lecture #23: Sections 12.4-12.6 in 5th ed. (4th ed: 11.4-11.6)

Topics: I. pH of salt solutions

II. Buffers!

I. pH of salt solutions

A salt is formed by the neutralization of an acid by a base.

HCl + NaOH gives NaCl and H2O

The pH of salt in water is not always .

Salts that contain the conjugate acids of weak bases produce acidic aqueous solutions; so do
salts that contain small, highly charged metal cations (e.g. Fe3+).

(Note: all Group 1 and 2 metals (e.g. Li+, Ca+2) and all metal cations with charge +1 (e.g. Ag+1)
are neutral.)

Salts that contain the conjugate bases of weak acids produce basic aqueous solution.

1) NH4Cl (aq) will produce a(n) solution.

NH4+ Is NH4+ a conjugate acid of a weak base and

therefore a weak acid? Ka = 5.6 x 10-10

Is NH3 a weak base? Kb = 1.8 x 10-5

Cl- Is Cl- a conjugate base of a weak acid and

therefore a weak base?

Is HCl a weak acid? Ka = 107

2) NaCH3COO (aq) will produce a(n) solution. Ka of CH3COOH is 1.76 x 10-5

Na+ Is Na+ a conjugate acid of a weak base and therefore acidic?

CH3COO- Is CH3COO- a conjugate base of a weak acid and therefore basic?

Is CH3COOH is weak acid?

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3) General rule for compound XY

X+ Is X+ a conjugate acid of a weak base? If yes, then acidic; If no, neutral

Y- Is Y- a conjugate base of a weak acid? If yes, then basic; If no, neutral

Overall: acidic+neutral=acidic; basic+neutral=basic;neutral+neutral=neutral

II. BUFFERS!

A buffer solution is any solution that maintains an approximately pH

despite small additions of acid and base.

An acid bufferFRQVLVWVRIDDQGLWVVXSSO ied as a salt.

It buffers on the acidic side of neutral.

A base buffer: consists of a weak base and its conjugate acid supplied as a salt. It buffers on
the basic side of neutral.

Acid Buffer Example: Mix acetic acid with an acetate salt and get dynamic equilibrium:

CH3COOH (aq) + H2O (l) H3O+ (aq) + CH3CO2- (aq)

What happens if strong acid is added to a solution containing approximately equal amounts
of CH3CO2- and CH3COOH?
• UHDFWLRQ
• The added H3O ions are effectivel \DQGWKHS+VWD\VFRQVWDQW
+

What happens if OH- base is added?

• The base removes a proton from CH3COOH to form H2O and CH3CO2- molecules.
• 7KHDGGHGLRQVDUHHIIHFWLYHOy removed and the pH stays constant.

Acid buffer action: The weak acid, HA, transfers protons to OH- ions supplied by strong
base. The conjugate base, A-, of the weak acid accepts protons from the H3O+ ions supplied
by a strong acid.

A strong acid and the salt of its conjugate base don't make a good buffer. Why?

Base Buffer Example: NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

When strong acid is added, NH3 accepts protons from incoming acid to make NH4+. When
strong base is added, NH4+ donates a proton to form NH3 and H2O.

pH remDLQVWKH

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Base buffer action: The weak base, B, accepts protons supplied by strong acid.
The conjugate acid, BH+, of the weak base transfers protons to the OH- ions supplied by a
strong base.

A buffer is a mixture of weak conjugate acids and bases that stabilize the pH of a solution
by providing D or for protons.

Buffers are important in biology! Blood is buffered in the range of 7.35-7.45. Buffering agents:
H2CO3/HCO3-

Sample Buffer Problem: Suppose 1.00 mol of HCOOH and 0.500 mol of NaHCOO are added
to water and diluted to 1.0 L. Calculate the pH. (Ka = 1.77 x 10-4)

HCOOH + H2O H3O+ + HCOO-

initial molarity 1.00 0 0.500
change in molarity -x +x +x
equilibrium molarity

Ka = 1.77 x 10-4 =

Using approximation that x is small compared to 1.00 and 0.500,

Ka = 1.77 x 10-4 =

x= 3.54 x 10-4 M

Check assumption

3.54 x 10-4 =

pH =

Now –Calculate the pH given that 0.100 mol of a strong acid (HCl) had been included in the
1.0 L solution.

Because 0.100 mol of HCl UHDFWVZLWKQXPber of moles of HCOO- to form

Poles of HCOOH:

For HCOO-, 0.500 mol - 0.100 mol Pol [HCOO-] = 0.400 mol/1.0 L =0.400 M

For HCOOH, 1.00 mol + 0.100 mol Pol [HCOOH] = 1.10 mol/1.0 L =1.10 M

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 HCOOH + H2O H3O+ + HCOO-
initial molarity
change in molarity
equilibrium molarity

Ka = 1.77 x 10-4=

Using approximation that x is small,

Ka = 1.77 x 10-4= x= 4.87 x 10-4

Check assumption (5% rule)

pH = -log [H3O+] = 3.31

So addition of 0.10 mol of strong acid only changed pH from 3.45 to 3.31!

Designing a Buffer

One must consider the relationship between the ratio of [HA] to [A-], pKa, and pH in
designing a buffer.
[H O+][A-]
HA (aq) + H2O <---> H3 O+ (aq) + A- (aq) Ka = [H3 O+][A-]
HA (aq) + H2O <---> H3 O+ (aq) + A- (aq) Ka = 3
[HA]
[HA]

Rearrange: [H3O+] = Ka x [HA]

Rearrange: [H3O+] = Ka x [HA]
[A-]
[A-]
[HA]
Take logarithms of both sides: log [H3O+] = log Ka + log [HA]
Take logarithms of both sides: log [H3O+] = log Ka + log [A-]
[A-]
[HA]
Multiply by (-) : -log [H3O+] = -log Ka - log [HA]
Multiply by (-) : -log [H3O+] = -log Ka - log [A-]
[A-]
[HA]
That is: pH = pKa - log [HA]
That is: pH = pKa - log [A-]
eq
[A-]
eq
The values of [HA] and [A-] in the equation are at equilibrium.

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However, a weak acid HA typically loses only a tiny fraction of its protons.

Likewise, a weak base A- typically only accepts a tiny fraction of protons.

So initial concentration is approximately __ to equilibrium concentration

~ pK - log [HA]0
So pH = a Henderson-Hasselbalch Equation
[A-]0

initial

This assumption is valid when [H3O+@LVFRPpared to [HA] and [A-] (i.e. less
than 5%).

Example: Design a buffer system with pH 4.60.

Acetic acid is suitable with a pKa of 4.75

A buffer solution is most effective in the range of pKa ±1

pH = pKa - log [CH3COOH]0
[CH3COO-]0

[CH3COOH]0
log = pKa - pH = 4.75 - 4.60 = 0.15
[CH3COO-]0

[CH3COOH]0
- = 100.15 = 1.4
[CH3COO ]0

The ratio is more important than the amounts used.

However, the amRXQWVGRDIIHFWWKHFDSDFLW\RIWKHEXIIHUWRFKDQJHVLQS+

Higher concentrations = more resistance to change.

If you use too low concentrations, the Henderson-Hasselbalch equation won’t be valid.

For pH 4.60, [H3O+] is 2.5 x 10-5.

2.5 x 10-5 x 100% < 5% need concentration > 5.0 x 10-4 M

[HA] or [A-]