ELECTROLYTIC PROPERTIES

An electrolyte is a substance that, when dissolved in water, results in a solution that can conduct electricity. A nonelectrolyte is a substance that, when dissolved, results in a solution that does not conduct electricity.

nonelectrolyte

weak electrolyte

strong electrolyte

METHOD OF DISTINGUISHING BETWEEN ELECTROLYTES AND NONELECTROLYTES

A pair of inert electrodes (Cu or Pt) is immersed in a beaker of water. To light the bulb, electric current must flow from one electrode to the other, thus completing the circuit. By adding NaCl (ionic compound), the bulb will glow. NaCl breaks up into Na+ and Cl- ions when dissolves in water. Na+ are attracted to the negative electrode. Cl- are attracted to the positive electrode. The movement sets up an electric current that is equivalent to the flow of electrons along a metal wire.

 Strong Electrolyte 100% dissociation (breaking up of compound into cations and anions
NaCl (s) H2O Na+ (aq) + Cl- (aq)

Weak Electrolyte not completely dissociated

CH3COOH CH3COO- (aq) + H+ (aq)

A reversible reaction. The reaction can occur in both directions.

 Hydration is the process in which an ion is surrounded by water molecules arranged in a specific manner. Hydration helps to stabilize ions and prevents cations from combining with anions.

dd+ d+

H2O

Nonelectrolyte does not conduct electricity?

No cations (+) and anions (-) in solution

C6H12O6 (s) H2O C6H12O6 (aq)

PROPERTIES ACIDS
Have a sour taste. - Vinegar owes its taste to acetic acid. - Citrus fruits contain citric acid. Cause color changes in plant dyes. React with certain metals to produce hydrogen gas. 2HCl (aq) + Mg (s) MgCl2 (aq) + H2 (g)

React with carbonates and bicarbonates to produce carbon dioxide gas 2HCl (aq) + CaCO3 (s) CaCl2 (aq) + CO2 (g) + H2O (l)

Aqueous acid solutions conduct electricity.

PROPERTIES OF BASES
Have a bitter taste. Feel slippery. Many soaps contain bases. Cause color changes in plant dyes. Aqueous base solutions conduct electricity. Examples:

ROLE OF WATER TO SHOW PROPERTIES OF ACIDS

Anhydrous pure acid (without water) does not show acidic properties. In dry form, acids exist as neutral covalent molecules. Dry acids do not dissociate to form hydrogen ion (H+). When a pure acid is dissolved in water, it will show the properties of acids. This is because acids will dissociate in water to form H+ or hydroxonium/hydronium ion, H3O+ which are free to move. For example: i) HCl in liquid methylbenzene (organic solvent) - does not show acidic properties. ii) HCl in water show acidic properties

ROLE OF WATER TO SHOW PROPERTIES OF ALKALI

Dry base does not show alkaline properties. A base in dry form, contains hydroxide ions (OH-) that are not free to move. Thus, the alkaline properties cannot be shown. In the presence of water, bases can dissociate in water to form hydroxide ions, OH-, which are free to move. Thus, alkaline properties are shown. For example: i) ammonia in tetrachlomethane (organic solvent) do not show alkaline properties ii) ammonia in water show alkaline properties

DEFINITION OF ACID AND BASE

Arrhenius

BrnstedLowry

Lewis

DEFINITION OF ACID AND BASE BY ARRHENIUS

Arrhenius acid is a substance that produces H+ (hydrogen ion) or hydronium ion (H3O+) in water

Arrhenius base is a substance that produces OH- in water

Examples of acid: CO2 (g) + H2O (l) H2CO3 (aq) + H2O(l) nonmetal oxides + H2O Examples of bases: H2CO3 (aq) H3O+ (aq) + HCO3- (aq) acid

NaOH (s)
N2H4 (aq) + H2O

Na+ (aq) + OH- (aq)

N2H5+ (aq) + OH- (aq) bases 2NaOH (aq)

metal oxides + H2O Na2O (s) + H2O (l)

* Limited only to aqueous solutions

DEFINITION OF ACID AND BASE BY BRNSTED-LOWRY

A Brnsted acid is a proton donor A Brnsted base is a proton acceptor Example:
HCl (aq) +H2O (l) H3O+ (aq) + Cl- (aq)

acid

base

acid

base

HCl is a acid because it donates proton to H2O H2O is a base because it accepts proton from HCl A Brnsted acid must contain at least one ionizable proton!

Brnsted acids and bases

Conjugate acid-base pair: i) Conjugate base of a Brnsted acid - the species that remains when one proton has been removed from the acid ii) Conjugate acid - addition of a proton to a Brnsted base

Examples: HCl (aq) +H2O (l) acid1 base2 H3O+ (aq) + Cl- (aq) acid2 base1

Cl- is a conjugate base of HCl and HCl is a conjugate acid of Cl-

H2O is a base conjugate of H3O+ and H3O+ is a acid conjugate of

H2 O

NH3 (aq) + H2O (l)

base1 acid2

NH4+ (aq) + OH- (aq)

acid1 base2

subscripts 1 and 2 = two conjugate acid-base pair

 When a strong acid react with a strong base in Brnsted acid-base

reaction, it will give a weak conjugate acid and conjugate base. Examples: HCl (aq) + H2O (l) strong acid strong base NH3 (aq) + H2O (l) Weak base weak acid H3O+ (aq) + Cl- (aq) weak conjugate weak conjugate acid base NH4+ (aq) + OH- (aq) strong conjugate strong conjugate acid base

H2O can function as acid or base which called amphoteric Amphoteric or amphiprotic substance is one that can react as either an acid or base

Identify each of the following species as a Brnsted acid, base, or both. (a) HI, (b) CH3COO-, (c) H2PO4-

HI (aq)

H+ (aq) + I- (aq)

Brnsted acid

CH3COO- (aq) + H+ (aq)

H2PO4- (aq)

CH3COOH (aq)

Brnsted base

H+ (aq) + HPO42- (aq) H3PO4 (aq)

Brnsted acid Brnsted base

H2PO4- (aq) + H+ (aq)

DEFINITION OF ACID AND BASE BY LEWIS

A Lewis acid is a substance that can accept a pair of electrons

A Lewis base is a substance that can donate a pair of electrons

+ OH acid base H+

H O H H + H N H H

H+ + acid

H base

H N H

Examples of Lewis Acids and Bases reactions: a) F F B F acid + H N H F F B F H N H H

H base

b) Ag+ (aq) + 2NH3 (aq) acid base c) Cd+ (aq) + 4I- (aq) acid base

Ag(NH3)2+ (aq) CdI2-4 (aq)

d) Ni (s) + 4CO (g)

acid base

Ni(CO)4 (g)

TYPES OF ACIDS-BASES
Acids i) Strong acids: - Acids that completely ionized in solution. - Example: HCl (aq) H+ (aq) + Cl- (aq) ii) Weak acids - Acids that incompletely ionized in solution - Example: CH3COOH (aq) CH3COO- (aq) + H+ (aq)

Monoprotic acid: - each unit of the acid yields one hydrogen ion upon ionization
HCl HNO3 H+ + ClH+ + NO3Strong electrolyte, strong acid

Strong electrolyte, strong acid

Weak electrolyte, weak acid

CH3COOH

H+ + CH3COO-

Diprotic acid: - each unit of the acid gives up two H+ ions, in two separate steps H2SO4 H+ + HSO4Strong electrolyte, strong acid Weak electrolyte, weak acid

HSO4-

H+ + SO42-

Triprotic acids: - yield three H+ ions

H3PO4 H2PO4HPO42H+ + H2PO4H+ + HPO42H+ + PO43Weak electrolyte, weak acid Weak electrolyte, weak acid Weak electrolyte, weak acid

 Bases i) Strong bases: - Bases that completely ionized in solution. - Example: NaOH (s) Na+ (aq) + OH- (aq) ii) Weak bases - bases that incompletely ionized in solution - Example: NH3 (aq) + H2O (l) NH4+ (aq) + OH- (aq)

Acids and bases as electrolytes

Strong acids such as HCl and HNO3 are strong electrolytes, while weak acid such as acetic acid (CH3COOH) is a weak electrolyte.
HCl (aq) + H2O (l) HNO3 (aq) + H2O (l) HClO4 (aq) + H2O (l) H2SO4 (aq) + H2O (l) H3O+ (aq) + Cl- (aq) H3O+ (aq) + NO3- (aq) H3O+ (aq) + ClO4- (aq) H3O+ (aq) + HSO4- (aq)

Acids and bases as electrolytes

Strong Acids are strong electrolytes

HCl (aq) + H2O (l)

HNO3 (aq) + H2O (l) HClO4 (aq) + H2O (l) H2SO4 (aq) + H2O (l)

H3O+ (aq) + Cl- (aq)

H3O+ (aq) + NO3- (aq) H3O+ (aq) + ClO4- (aq) H3O+ (aq) + HSO4- (aq)

Weak Acids are weak electrolytes HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

HNO2 (aq) + H2O (l) HSO4- (aq) + H2O (l)

H2 O (l) + H 2 O (l)

H3O+ (aq) + NO2- (aq) H3O+ (aq) + SO42- (aq)

H3O+ (aq) + OH- (aq)

Strong Bases are strong electrolytes H2O + NaOH (s) Na (aq) + OH- (aq) H2O + KOH (s) K (aq) + OH- (aq) H2O 2+ Ba(OH)2 (s) Ba (aq) + 2OH- (aq)

Weak Bases are weak electrolytes F- (aq) + H2O (l) NO2- (aq) + H2O (l) OH- (aq) + HF (aq) OH- (aq) + HNO2 (aq)

Conjugate acid-base pairs: The conjugate base of a strong acid has no measurable strength. H3O+ is the strongest acid that can exist in aqueous solution. The OH- ion is the strongest base that can exist in aqueous solution.

ACID-BASE PROPERTIES OF WATER

Can act either as a acid or as a base.
Water functions as a base with acids such as HCl and CH3COOH and function as acid in reaction with bases. Water is a very weak electrolyte and undergo ionization to a small extent:

H2O (l)

H+ (aq) + OH- (aq)

autoionization of water

The Ion Product of Water

H2 O (l) [H+][OH-] Kc = [H2O] Kc[H2O] = Kw = [H+][OH-] The ion-product constant (Kw) is the product of the molar concentrations of H+ and OH- ions at a particular temperature. Solution Is [H+] = [OH-] neutral H+ (aq) + OH- (aq) [H2O] = constant Kc = equilibrium constant

At 250C Kw = [H+][OH-] = 1.0 x 10-14

[H+] > [OH-]

[H+] < [OH-]

acidic
basic

What is the concentration of OH- ions in a HCl solution whose hydrogen ion concentration is 1.3 M? Kw = [H+][OH-] = 1.0 x 10-14 [H+] = 1.3 M

-14 K 1 x 10 w -15 M = = 7.7 x 10 [OH-] = [H+] 1.3

pH-A MEASURE OF ACIDITY

pH the negative logarithm of the hydrogen in concentration (in mol/L) pH = -log [H+] Solution Is neutral acidic basic At 250C [H+] = 1 x 10-7 [H+] > 1 x 10-7 [H+] < 1 x 10-7 [H+]

[H+] = [OH-] [H+] > [OH-] [H+] < [OH-] pH

pH = 7 pH < 7 pH > 7

Other important relationships

pOH = -log [OH-] [H+][OH-] = Kw = 1.0 x 10-14

-log [H+] log [OH-] = 14.00

pH + pOH = 14.00

pH Meter

1) The pH of rainwater collected in a certain region of the northeastern United States on a particular day was 4.82. What is the H+ ion concentration of the rainwater?
pH = -log [H+] [H+] = 10-pH = 10-4.82 = 1.5 x 10-5 M

2) The OH- ion concentration of a blood sample is 2.5 x 10-7 M. What is the pH of the blood?
pH + pOH = 14.00

pOH = -log [OH-] = -log (2.5 x 10-7) = 6.60

pH = 14.00 pOH = 14.00 6.60 = 7.40

CALCULATION OF pH FOR SOLUTION CONTAINING A STRONG ACID AND A SOLUTION OF A STRONG BASE

1) What is the pH of a 2 x 10-3 M HNO3 solution? HNO3 is a strong acid 100% dissociation. Start 0.002 M HNO3 (aq) + H2O (l) End 0.0 M 0.0 M 0.0 M H3O+ (aq) + NO3- (aq) 0.002 M 0.002 M

pH = -log [H+] = -log [H3O+] = -log(0.002) = 2.7 2) What is the pH of a 1.8 x 10-2 M Ba(OH)2 solution? Ba(OH)2 is a strong base 100% dissociation.

Start 0.018 M Ba(OH)2 (s) End 0.0 M

0.0 M 0.0 M Ba2+ (aq) + 2OH- (aq) 0.018 M 0.036 M

pH = 14.00 pOH = 14.00 + log(0.036) = 12.6

Weak Acids (HA) and Acid Ionization Constants

HA (aq) + H2O (l)
HA (aq)

H3O+ (aq) + A- (aq)

H+ (aq) + A- (aq)

[H+][A-] Ka = [HA]
Ka is the acid ionization constant

Ka

weak acid strength

1) What is the pH of a 0.5 M HF solution (at 250C)? HF (aq) H+ (aq) + F- (aq) [H+][F-] = 7.1 x 10-4 Ka = [HF]

HF (aq)
Initial (M) Change (M) 0.50 -x

H+ (aq) + F- (aq)
0.00 +x x 0.00 +x x

Equilibrium (M) 0.50 - x Ka = Ka x2 = 7.1 x 10-4 0.50 - x Ka << 1

0.50 x 0.50 x = 0.019 M

x2 0.50

= 7.1 x 10-4

x2 = 3.55 x 10-4

[H+] = [F-] = 0.019 M [HF] = 0.50 x = 0.48 M

pH = -log [H+] = 1.72

When can I use the approximation? Ka << 1 0.50 x 0.50

When x is less than 5% of the value from which it is subtracted. x = 0.019

0.019 M x 100% = 3.8% 0.50 M

Less than 5%

Approximation ok.

1) What is the pH of a 0.05 M HF solution (at 250C)? x2 Ka = 7.1 x 10-4 x = 0.006 M 0.05 More than 5% 0.006 M x 100% = 12% 0.05 M Approximation not ok.
Must solve for x exactly using quadratic equation or method of successive approximations.

Solving weak acid ionization problems:

1. Identify the major species that can affect the pH. In most cases, you can ignore the autoionization of water.

Ignore [OH-] because it is determined by [H+].

2. Use ICE to express the equilibrium concentrations in terms of single unknown x.

3. Write Ka in terms of equilibrium concentrations. Solve for x by the approximation method. If approximation is not valid, solve for x exactly. 4. Calculate concentrations of all species and/or pH of the solution.

1) What is the pH of a 0.122 M monoprotic acid whose Ka is 5.7 x 10-4?

HA (aq) Initial (M) Change (M) 0.122 -x H+ (aq) + A- (aq) 0.00 +x x Ka << 1 0.00 +x x 0.122 x 0.122

Equilibrium (M) 0.122 - x x2 = 5.7 x 10-4 Ka = 0.122 - x Ka x2 = 5.7 x 10-4 0.122

x2 = 6.95 x 10-5

x = 0.0083 M

0.0083 M x 100% = 6.8% 0.122 M

More than 5% Approximation not ok.

x2 = 5.7 x 10-4 Ka = 0.122 - x

ax2 + bx + c =0

x2 + 0.00057x 6.95 x 10-5 = 0

x = 0.0081
HA (aq)

-b b2 4ac x= 2a x = - 0.0081
H+ (aq) + A- (aq)

Initial (M)
Change (M)

0.122
-x

0.00
+x x

0.00
+x x

Equilibrium (M) 0.122 - x

[H+] = x = 0.0081 M pH = -log[H+] = 2.09

Weak Bases and Base Ionization Constants

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

[NH4+][OH-] Kb = [NH3]

Kb is the base ionization constant Kb

weak base strength

Solve weak base problems like weak acids except solve for [OH-] instead of [H+].

CONCENTRATION OF SOLUTION
The concentration of a solution is the amount of solute present in a given quantity of solvent or solution. M = molarity = moles of solute liters of solution

1) What mass of KI is required to make 500. mL of a 2.80 M KI solution?

M KI M KI

volume of KI solution
500. mL x 1L 1000 mL x

moles KI
2.80 mol KI 1 L soln

grams KI
= 232 g KI

166 g KI 1 mol KI

Preparing a Solution of Known Concentration

DILUTION OF SOLUTIONS
Dilution is the procedure for preparing a less concentrated solution from a more concentrated solution.

Dilution Add Solvent

Moles of solute before dilution (i) MiVi

Moles of solute after dilution (f) MfVf

EXAMPLE: 1) How would you prepare 60.0 mL of 0.200 M HNO3 from a stock solution of 4.00 M HNO3?
MiVi = MfVf
Mi = 4.00 M Mf = 0.200 M 0.200 M x 0.0600 L 4.00 M Vf = 0.0600 L Vi = ? L

Vi =

MfVf Mi

= 0.00300 L = 3.00 mL

Dilute 3.00 mL of acid with water to a total volume of 60.0 mL.

Concentration Units
The concentration of a solution is the amount of solute present in a given quantity of solvent or solution.
Percent by Mass (%w/w) % by mass =

mass of solute mass of solute + mass of solvent mass of solute = mass of solution
x 100%

x 100%

Percent by Volume (%v/v) Volume of solute x 100% % by volume = Volume of solution

Mole Fraction (X) moles of A XA = sum of moles of all components

Molarity (M) M = moles of solute liters of solution

Molality (m) m = moles of solute mass of solvent (kg)

VOLUMETRIC ANALYSIS (VA)

Quantitative analytical process based on measuring volumes. The most common form of VA is the titration, a process whereby a standard solution of known concentration is chemically reacted with a solution of unknown concentration in order to determine the concentration of the unknown.

TITRATIONS
In a titration a solution of accurately known concentration (standard solution) is added gradually added to another solution of unknown concentration until the chemical reaction between the two solutions is complete. Equivalence point the point at which the reaction is complete Indicator substance that changes color at (or near) the equivalence point Titrations can be used in the analysis of acid-base reactions H2SO4 + 2NaOH 2H2O + Na2SO4

PROCEDURE FOR THE TITRATION

Slowly add base to unknown acid UNTIL the indicator changes color

EXAMPLE: 1) What volume of a 1.420 M NaOH solution is required to titrate 25.00 mL of a 4.50 M H2SO4 solution?
WRITE THE CHEMICAL EQUATION! H2SO4 + 2NaOH
M

2H2O + Na2SO4
rxn M

volume acid

acid

moles red

coef.

moles base

base

volume base

25.00 mL x

4.50 mol H2SO4 1000 mL soln

2 mol NaOH 1 mol H2SO4

1000 ml soln 1.420 mol NaOH

= 158 mL

ACID-BASE TITRATIONS
Strong Acid-Strong Base Titrations NaOH (aq) + HCl (aq) OH- (aq) + H+ (aq) H2O (l) + NaCl (aq) H2O (l)

pH PROFILE OF THE TITRATION (TITRATION CURVE)

pH PROFILE OF THE TITRATION (TITRATION CURVE) Before addition of NaOH - pH = 1.00 When the NaOH added - pH increase slowly at first Near the equivalence point (the point which equimolar amounts of acid and base have reacted) - the curve rises almost vertically Beyond the equivalence point - pH increases slowly

CALCULATION OF Ph AT EVERY STAGE OF TITRATION

1) After addition of 10.0 mL of 0.100 M NaOH to 25.0 mL of 0.100 M HCl Total volume = 35.0 mL Moles of NaOH in 10.0 mL = 10.0 mL x 0.100 mol NaOH x 1L 1L NaOH 1000 mL = 1.00 x 10-3 mol Moles of HCl in 25.0 mL = 25.0 mL x 0.100 mol HCl x 1 L HCl = 2.50 x 10-3 mol 1L 1000 mL

Amount of HCl left after partial neutralization = (2.50 x 10-3)-(1.00 x 10-3) = 1.50 x 10-3 mol Concentration of H+ ions in 35.0 mL 1.50 x 10-3 mol HCl x 1000 mL = 0.0429 M HCl 35.0 mL 1L
[H+] = 0.0429 M, pH = -log 0.0429 = 1.37

2) After addition of 25.0 mL of 0.100 M NaOH to 25.0 mL 0f 0.100 M HCl [H+] = [OH-] = 1.00 x 10-7 pH = 7.00

3) After addition of 35.0 mL of 0.100 M NaOH to 25.0 mL of 0.100 mL of HCl

Total volume = 60.0 mL Moles of NaOH added = 35.0 mL x 0.100 mol NaOH x 1L 1 L NaOH 000 mL = 3.50 x 10-3 mol Moles of HCl in 25.0 mL solution = 2.50 x 10-3 mol After complete neutralization of HCl, no of moles of NaOH left = (3.50 x 10-3)-(2.50x10-3) = 1.00 x 10-3 mol Concentration of NaOH in 60.0 mL solution = 1.00 x 10-3 mol NaOH x 1000 mL 60.0 mL 1L = 0.0167 M NaOH [OH-] = 0.0167 M pOH = -log 0.0167 = 1.78 pH = 14.00 1.78 = 12.22

Exactly 100 mL of 0.10 M HNO2 are titrated with a 0.10 M NaOH solution. What is the pH at the equivalence point ? start (moles)

NO2- (aq) + H2O (l) end (moles) 0.01 0.01 Final volume = 200 mL [NO2-] = = 0.05 M 0.200 NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)
Initial (M) Change (M) 0.05 -x 0.00 +x x pOH = 5.98 0.00 +x x

0.01 0.01 HNO2 (aq) + OH- (aq) 0.0 0.0

Equilibrium (M) 0.05 - x [OH-][HNO2] x2 -11 = 2.2 x 10 Kb = = [NO2-] 0.05-x 0.05 x 0.05 x 1.05 x 10-6 = [OH-]

pH = 14 pOH = 8.02

Acid-Base Indicators
HIn (aq) H+ (aq) + In- (aq) [HIn] 10 Color of acid (HIn) predominates [In ]

[HIn] -) predominates Color of conjugate base (In 10 [In-]