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Course: B.Sc. I Subject: Chemistry I Unit: II

B sc i chemistry i u ii ionic equilibria in aqueous solution a

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Page 1: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Course: B.Sc. I

Subject: Chemistry I

Unit: II

Page 2: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Acids

Produce H+ (as H3O+) ions in water (the hydronium ion is a

hydrogen ion attached to a water molecule)

Taste sour

Corrode metals

React with bases to form a salt and water

pH is less than 7

Turns blue litmus paper to red “Blue to Red A-CID”

Page 4: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Bases

Produce OH- ions in water

Taste bitter, chalky

Feel soapy, slippery

React with acids to form salts and water

pH greater than 7

Turns red litmus paper to blue “Basic Blue”

Page 5: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Some Common Bases

NaOH sodium hydroxide lye

KOH potassium hydroxide liquid soap

Ba(OH)2 barium hydroxide stabilizer for plastics

Mg(OH)2 magnesium hydroxide “MOM” Milk of magnesia

Al(OH)3 aluminum hydroxide Maalox (antacid)

4

Page 6: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Concepts of acid-base theory

Page 7: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Acid/Base definitions

Definition #1: Arrhenius (traditional)

Acids – produce H+ ions (or hydronium ions H3O+)

Bases – produce OH- ions

Page 8: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Arrhenius Concept of Acids and BasesAccording to the Arrhenius concept of acids

and bases,

an Acid is a substance that, when dissolved in water, increases the concentration of hydronium ion or H+ ion (H3O

+ ).• the aqueous hydrogen ion is actually chemically

bonded to water, that is, H3O+.

• Chemists often use the notation H+(aq) for the H3O

+(aq) ion.

Page 9: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Arrhenius concept of basesA base, in the Arrhenius concept, is a

substance that, when dissolved in water, increases the concentration of hydroxide ion, OH-(aq).

Page 10: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Arrhenius acid is a substance that produces H+ (H3O+) in water

Arrhenius base is a substance that produces OH- in water

3

Page 11: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Limitations

Page 12: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases• According to the Brønsted-Lowry concept,

• An acid is the species donating the proton

in a proton-transfer reaction.

• A base is the species accepting the proton in a

proton-transfer reaction

Page 13: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Consider the reaction of NH3 and H20.

)aq(OH )aq(NH )l(OH )aq(NH 423

Page 14: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Consider the reaction of NH3 and H2O.

– In the forward reaction, NH3 accepts a proton

from H2O. Thus, NH3 is a base and H2O is an

acid.

)aq(OH )aq(NH )l(OH )aq(NH 423

H+

base acid

Page 15: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Consider the reaction of NH3 and H2O.

– In the reverse reaction, NH4+ donates a

proton to OH-. The NH4+ ion is the acid and

OH- is the base.

)aq(OH )aq(NH )l(OH )aq(NH 423

H+

baseacid

Page 16: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases Consider the reaction of NH3 and H2O.

– A conjugate acid-base pair consists of two

species in an acid-base reaction, one acid and

one base, that differ by the loss or gain of a

proton.

)aq(OH )aq(NH )l(OH )aq(NH 423

base acid

– The species NH4+ and NH3 are a conjugate

acid-base pair.

Page 17: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases Consider the reaction of NH3 and H2O.

– The Brønsted-Lowry concept defines a species

as an acid or a base according to its function in

the proton-transfer reaction.

)aq(OH )aq(NH )l(OH )aq(NH 423

base acid

– Here NH4+ is the conjugate acid of NH3 and

NH3 is the conjugate base of NH4+.

Page 18: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases Some species can act as an acid or a base.

)l(OH)aq(CO)aq(OH)aq(HCO 2

2

33

–H+

– An amphoteric species is a species that can act

either as an acid or a base (it can gain or lose a

proton).

– For example, HCO3- acts as a proton donor (an acid) in

the presence of OH-

Page 19: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases Some species can act as an acid or a base.

– An amphoteric species is a species that can act

either as an acid or a base (it can gain or lose a

proton).

– Alternatively, HCO3 can act as a proton acceptor

(a base) in the presence of HF.

)aq(F)aq(COH)aq(HF)aq(HCO 323

H+

Page 20: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases The amphoteric characteristic of water is important in

the acid-base properties of aqueous solutions.

– Water reacts as an acid with the base NH3.

)aq(OH)aq(NH)l(OH)aq(NH 423

H+

Page 21: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases The amphoteric characteristic of water is important in

the acid-base properties of aqueous solutions.

– Water can also react as a base with the acid

HF.

)aq(OH)aq(F)l(OH)aq(HF 32

H+

Page 22: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Brønsted-Lowry Concept of Acids and Bases In the Brønsted-Lowry concept:

2. Acids and bases can be ions as well as molecular

substances.

3. Acid-base reactions are not restricted to aqueous

solution.

4. Some species can act as either acids or bases

depending on what the other reactant is.

1. A base is a species that accepts protons; OH- is only

one example of a base.

Page 23: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Lewis Concept of Acids and Bases The Lewis concept defines an acid as an electron

pair acceptor and a base as an electron pair donor.

– This concept broadened the scope of acid-

base theory to include reactions that did not

involve H+.

Page 24: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Lewis Concept of Acids and Bases The reaction of boron trifluoride with ammonia is an

example.

– Boron trifluoride accepts the electron pair, so it is a

Lewis acid. Ammonia donates the electron pair,

so it is the Lewis base.

+ N

H

H

H:

::

: B

F

F

F

: :

::

::

::

: B

F

F

F

: :

::

:: N

H

H

H

Page 25: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Relative Strength of Acids and Bases The Brønsted-Lowry concept introduced the idea of

conjugate acid-base pairs and proton-transfer reactions.

– The stronger acids are those that lose their

hydrogen ions more easily than other acids.

– Similarly, the stronger bases are those that hold

onto hydrogen ions more strongly than other

bases.

Page 26: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Relative Strength of Acids and Bases The Brønsted-Lowry concept introduced the idea of

conjugate acid-base pairs and proton-transfer reactions.

– If an acid loses its H+, the resulting anion is now in

a position to reaccept a proton, making it a

Brønsted-Lowry base.

– It is logical to assume that if an acid is considered

strong, its conjugate base (that is, its anion) would be

weak, since it is unlikely to accept a hydrogen ion.

Page 27: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Relative Strength of Acids and Bases Consider the equilibrium below.

– In this system we have two opposing Brønsted-

Lowry acid-base reactions.

– In this example, H3O+ is the stronger of the two

acids. Consequently, the equilibrium is skewed

toward reactants.

(aq)OHC(aq)OH 2323

)l(OH)aq(OHHC 2232 acid acidbase base

conjugate acid-base pairs

Page 28: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Relative Strength of Acids and Bases Consider the equilibrium below.

– This concept of conjugate pairs is fundamental to

understanding why certain salts can act as acids or

bases.

(aq)OHC(aq)OH 2323

)l(OH)aq(OHHC 2232 acid acidbase base

conjugate acid-base pairs

Page 29: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Self-ionization of Water Self-ionization is a reaction in which two like

molecules react to give ions.

In the case of water, the following equilibrium

is established.

)aq(OH)aq(OH )l(OH)l(OH 322

– The equilibrium-constant expression for this

system is:

22

3c

]OH[

]OH][OH[K

Page 30: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Self-ionization of Water Self-ionization is a reaction in which two like

molecules react to give ions.

– The concentration of ions is extremely

small, so the concentration of H2O remains

essentially constant. This gives:

]OH][OH[K]OH[ 3c2

2

constant

Page 31: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Self-ionization of Water– We call the equilibrium value for the ion product

[H3O+][OH-] the ion-product constant for water,

which is written Kw.

]OH][OH[K 3w

– At 25 oC, the value of Kw is 1.0 x 10-14.

– Like any equilibrium constant, Kw varies with

temperature.

Page 32: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Self-ionization of Water– Because we often write H3O

+ as H+, the ion-

product constant expression for water can be

written:

]OH][H[Kw

– Using Kw you can calculate the concentrations of

H+ and OH- ions in pure water.

Page 33: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

Self-ionization of Water These ions are produced in equal numbers in pure

water, so if we let x = [H+] = [OH-]

– Thus, the concentrations of H+ and OH- in pure

water are both 1.0 x 10-7 M.

– If you add acid or base to water they are no longer

equal but the Kw expression still holds.

C 25at )x)(x(100.1o14

714100.1100.1x

Page 34: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH of a Solution Although we can quantitatively describe the acidity of

a solution by its [H+], it is often more convenient to give acidity in terms of pH.

– The pH of a solution is defined as the negative

logarithm of the molar hydrogen-ion concentration.

]Hlog[pH

Page 35: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH of a Solution For a solution in which the hydrogen-ion

concentration is 1.0 x 10-3, the pH is:

– Note that the number of decimal places in

the pH equals the number of significant

figures in the hydrogen-ion concentration.

00.3)100.1log( 3 pH

Page 36: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH of a Solution In a neutral solution, whose hydrogen-ion concentration

is 1.0 x 10-7, the pH = 7.00.• For acidic solutions, the hydrogen-ion

concentration is greater than 1.0 x 10-7, so the

pH is less than 7.00.

• Similarly, a basic solution has a pH greater

than 7.00.

• Figure shows a diagram of the pH scale and the

pH values of some common solutions.

Page 37: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH Scale

3

Page 38: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

A Problem to Consider A sample of orange juice has a hydrogen-ion

concentration of 2.9 x 10-4 M. What is the pH?

]Hlog[pH

)109.2log(pH4

54.3pH

Page 39: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

A Problem to Consider The pH of human arterial blood is 7.40. What is the

hydrogen-ion concentration?

)pHlog(anti]H[

)40.7log(anti]H[

M100.410]H[840.7

Page 40: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH of a Solution A measurement of the hydroxide ion concentration,

similar to pH, is the pOH.

– The pOH of a solution is defined as the

negative logarithm of the molar hydroxide-

ion concentration.

]OHlog[pOH

Page 41: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH of a Solution A measurement of the hydroxide ion concentration,

similar to pH, is the pOH.

– Then because Kw = [H+][OH-] = 1.0 x 10-14

at 25 oC, you can show that

00.14pOHpH

Page 42: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

A Problem to Consider An ammonia solution has a hydroxide-ion

concentration of 1.9 x 10-3 M. What is the pH of the solution?

You first calculate the pOH:

72.2)109.1log(pOH3

Then the pH is:

28.1172.200.14pH

Page 43: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH of a Solution The pH of a solution can accurately be measured using

a pH meter

– Although less precise, acid-base indicators are

often used to measure pH because they usually

change color within a narrow pH range.

Page 44: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

The pH Meter

Page 45: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

THE COMMON–ION EFFECT

Page 46: B sc  i chemistry i u ii ionic equilibria in aqueous solution a
Page 47: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

SELECTIVE PRECIPITATION

Page 48: B sc  i chemistry i u ii ionic equilibria in aqueous solution a
Page 49: B sc  i chemistry i u ii ionic equilibria in aqueous solution a

1. General chemistry by Ebbing Darell,3rd

edition

2. Essentials of physical chemistry by bahland tuli ,3 rd edition

3.https:// sites.google.com

4. https://www.mhhe.com

Presentation

of Lecture

Outlines,

16–49