Lecture #2: Ionic Equilibrium

Overview: Acid-Base Concept Acid

There exist different definitions for an acid and a base Arrhenius Definition An acid is a substance that produces hydroxonium ion (H3O+) as the only positively charged ion A base is a substance the produces (OH-) as the only negatively charged ion

AcidAcid-Base Concept

The Arrhenius theory accounts for the many acids and bases that exist One limitation with the theory is that it is only applicable to aqueous solutions. As a result a molecule like ammonia (alkaline gas) would not be classified as a base

A more general definition for acid and base were later proposed by 2 Scientists, Johannes Brnsted and Thomas Lowry

AcidAcid-Base Concept

Brnsted-Lowry Theory An acid is any substance (molecule or ion) that transfers a proton to another substance A base is any substance (molecule or ion) that accepts a proton HA
H+ donor

B
H+ acceptor

BH+
H+ donor

AH+ acceptor

AcidAcid-Base Concept

Chemical species whose formulae differ by one proton are said to be conjugate acid-base pairs

AcidAcid-Base Concept

Exercise Write balanced equation for the dissociation of each of the Brnsted-Lowry acids below (a) H2SO4 case sulphuric acid

What is the conjugate base of the acid in each

AcidAcid-Base Concept

Write balanced equation for the dissociation of each of the Brnsted-Lowry bases below (a) HCO32What is the conjugate acid for the base in each case

Acid and Base Strength

A strong acid (strong base) is completely dissociated in aqueous solution Therefore the acid (base) dissociation equilibrium of a strong acid (strong base) lies entirely to the right and as such only ions are present in the solution HCl (aq) H+ (aq) + NaOH (aq) Na+
(aq)

Cl-

(aq) (aq)

+ OH-

Source: http://wikis.lawrence.edu/display/CHEM/Acids+and+Bases-Davis

Acid and Base Strength

A weak acid (weak base) is partially dissociated in aqueous solution Only a small fraction of the of the molecule is transferred to ions CH3COOH (aq) CH3COO- (aq) + H+ (aq)

Acid and Base Strength

Source: http://wwwchem.csustan.edu/chem3070/images/acetic.gif

Relative Strength of Conjugate Acid-Base Pairs Acid-

Dissociation of Water
Water is amphoteric, i.e. it can act both as an acid and a base In the presence of an acid water act as a base and in the present of a base water act as a acid

HCl (aq) +
proton donor

H2O(l) H3O+(aq) + Cl- (aq)

proton acceptor

NH3(aq) + H2O(l)
proton acceptor proton donor

NH4+(aq) + OH-(aq)

Pure water can also act as an acid and a base with itself H2O(l) + H2O (l) 2H2O (l) H3O+(aq) + OH-(aq) H3O+(aq) + OH-(aq)

Changing the equilibrium constant Kc to Kw Kw = [H3O+][OH-] Experiment done at 25C have shown that [H3O+] = 1.0 x 10-7 Since the dissociation of water produces equal volumes of [H3O+] and [OH-] then Kw = (1.0 x 10-7)(1.0 x 10-7) = 1.0 x 10-14

A neutral solution - [H3O+] = [OH-] = 1.0 x 10-7 Acidic solutions - [H3O+] > [OH-] [H3O+] > 1.0 x 10-7 [OH-] < 1.0 x 10-7 Basic solutions - [H3O+] < [OH-] [H3O+] < 1.0 x 10-7 [OH-] > 1.0 x 10-7

In all solutions at 25C - [H3O+] [OH-] = Kw = 1.0 x 10-14

 1.

Exercise The concentration of H3O+ ions in a sample of lemon juice is 2.5 x 10-3 M. Calculate the concentration of OHions, and classify the solution as neutral, acidic, or basic The concentration of OH- in a sample of sea water is 5 x 10-6 M. Calculate the concentration of H3O+ ions, and classify the solution

2.

3.

At 50C the Kw is 5.5 x 10-14. What are the concentrations of H3O+ and OH- ions in a neutral solution at 50C.

pH Scale

pH (power of hydrogen) pH = -log [H3O+] It is a logarithmic scale that is used to specify the acidity of a solution pH < 7 acidic pH > 7 alkaline pH = 7 - neutral

pH Scale
pOH power of hydroxide ion pH + pOH = 14

Source: http://academic.cuesta.edu/gbaxley/chem1A/notes/ph_scale_2.jpg

Calculate the pH of the following solution and indicate whether the solution is acidic or basic [H3O+] = 1.8 x 10-4 M pH = -log [H3O+] pH = -log (1.8 x 10-4 ) pH = -(- 3.74) pH = 3.74

N.B when you take the log of a quantity the result should have the same number of decimal places as significant figures of the original quantity

 1.

Exercise Calculate the pH of a solution with a [H3O+] of 9.5 x 10-9 M Calculate the [H3O+] for a solution of a pH of 4.80 Calculate the [OH-] for a solution with a pH of 3.66

2.

3.

Complete the table below

[H3O+] 1 x 10-14 [OH-] pH Acidic or basic

4.00

5.5 x 10-3

3.2 x 10-6

4.8 x 10-9

7.55

Equilibria Solutions of Weak Acids

Recap: strong acids are completely dissociated in aqueous solutions and weak acids are partially dissociated in aqueous solutions HA (aq) + H2O(l) Kc = [H3O+][A-] [HA][H2O] Ka = acid-dissociation constant Ka = Kc [H2O] = [H3O+][A-] [HA] The larger the Ka value the stronger the acid H3O+ (aq) + A- (aq)

The pH of a 0.250 M HF is 2.036. What is the value of Ka for the hydrofluoric acid solution? HF (aq) + H2O(l) Ka = [H3O+][F-] [HF] pH = - log [H3O+] [H3O+] = antilog (-pH) = 10 pH = 9.2 x 10-3 M H3O+ (aq) + F- (aq)

Since mole ration of H3O+ : F- is 1:1; [F-] = 9.2 x 10-3 M The [HF] at equilibrium = 0.25 - 0.00920 = 0.241 M

Ka = (9.20 x 10-3)(9.20 x 10-3) 0.241 Ka = 3.52 x 10-4


1.

Exercise
The pH of 0.1 M HClO is 4.23. Calculate the Ka for the hyperchlorous acid. The pH of 0.040 M hypobromous acid (HOBr) is 5.05. Set up the equilibrium equation for the dissociation of HOBr, and calculate the acid dissociation constant.

2.

Equilibria Solutions of Weak Bases

Kb dissociation constant of a weak base NH3 (aq) + H2O (l) Kb = [NH4+ ][OH- ] [NH3] NH4+(aq) + OH-(aq)

Exercise
1.

Codeine (C8H21NO3), a drug used in painkillers and cough medicines, is a naturally occurring amine that has a Kb = 1.6 x 10-6. Calculate the pH and the concentration of all species present in a 0.0012 M solution of codeine. Use cod as the abbreviation for codeine and codH+ for the conjugated acid.

2.

Calculate the pH and the concentration of all the species present in 0.40 M NH3 (Kb = 1.8 x 10-5)

Acid Base Titrations

When an acid reacts with a base, salt and water is formed This type of reaction is called neutralization There exist four types of neutralization reactions Strong acid strong base Weak acid strong base Strong acid weak base Weak acid weak base

(a)

(b) (c) (d)

Acid Base Titrations

An acid-base titration is a neutralization reaction that is performed in the lab to determine an unknown concentration of acid or base The solution containing a known concentration is added from a burette to a second solution containing an unknown concentration of acid or base The progress of the reaction is monitored using a pH meter or by observing the colour of a suitable indicator

Acid Base Titrations

A typical pH graph has a sigmoid shape

Mid way the vertical region of the graph is known as the equivalence point

Source: http://www.chemguide.co.uk/physical/acidbaseeqia/phcurves.html

Acid Base Titrations

At the equivalence point there are equal numbers of H+ and OH- ion concentration The equivalence point varies depending on the acidbase combination used As a result an appropriate indicator has to be used

Acid Base Titrations

Indicators are organic compounds that change colour in response to a pH change The strength of the acid and base used in neutralization will determine the type of indicator used

Indicator

pH

Neutral colour

Acid base combination

Litmus solution

Purple

Strong acid strong base

Phenolphthalein

9.7

Colourless

Strong base weak acid

Methyl orange

3.7

Yellow

Strong acid weak base

Solubility Product

The equilibrium equation for the dissolution reaction is called the equilibrium constant Ksp Ksp solubility product constant CaF2(s) Ca2+ (aq) + 2F-(aq) (Heterogeneous mixture) The Ksp = [Ca2+][F-]2 The Ksp is always equal to the product of the equilibrium concentrations of all the ions on the right side of the chemical equation, with the concentration of each ion raised to the power of its coefficient in a balanced equation The concept of solubility product constant applies only to sparingly soluble compounds. It would not apply to vey soluble compounds.


1.

Exercise
A particular saturated solution of silver chromate, Ag2CrO4, has [Ag+] = 5.0 x 10-5M and [CrO42-] = 4.4 x 10-4 M. What is the value of Ksp for Ag2CrO4?

2.

A saturated solution of Ca3(PO4)2 has [Ca2+] = 2.01 x 10-8 M and PO43- = 1.6 x 10-5M. Calculate the Ksp for Ca3(PO4)2

3.

The solubility of lead(II)chloride at 298 K is 0.834g per 100 cm3 of water. Find the solubility product of lead(II)chloride at this temperature

Common Ion Effect

The common ion effect can be defined as that effect which causes the repression of the dissociation of a compound by the addition of a common cation or anion The presence of the common ion affect the solubility of a salt

Common Ion Effect

e.g. CaF2(s)

Ca2+ (aq) + 2F-(aq)

If F- is added from another source (e.g NaF) then this will result in an increase in the concentration of F- and according to Le Chateliers principle the equilibrium will shift to the left producing more CaF2(s) As a result the solubility of the salt CaF2(s) decreases This is known as the common ion effect

Buffers

Buffers are solutions that resist changes in pH Buffers do this by neutralizing added acid or base Blood is a buffer that resists changes in pH. If the pH of blood drops below 7.0 or increase beyond 7.8 we would die Like all buffers blood contains a significant amounts of both weak acid and conjugate base When additional base is added to blood the acid reacts with the base neutralizing it. In addition if acid is added to blood the conjugate base reacts with the acid neutralizing it

Buffers

Blood contains an carbonic acid- bicarbonate buffer H+(aq) + HCO3-(aq) H20(l) + CO2(g) The Henderson-Hasselbalch equation is used to calculate the pH of a buffer solution pH = pKa + log ([base]/[acid] pKa = -log Ka

 1.

Exercise Calculate the pH of a buffer solution made from 0.20 M HC2H3O2 and 0.50 M C2H3O2- that has an acid dissociation constant for HC2H3O2 of 1.8 x 10-5.

pH = pKa + log ([A-]/[HA]) pH = pKa + log ([C2H3O2-] / [HC2H3O2]) pH = -log (1.8 x 10-5) + log (0.50 / 0.20) pH = -log (1.8 x 10-5) + log (2.5) pH = 4.7 + 0.40 pH = 5.1

2. Use the Henderson-Hasselbalch equation to calculate the pH of a buffer solution that is 0.25 M in formic acid (HCOOH) and 0.50 M in sodium formate (HCO2Na). Ka of formic acid = 1.80 x 10-4.