BrØnstead

– Lowry acids and bases

An acid is a proton donor

A base is a proton acceptor

Proton transfer reac7on

HCl (aq) H3O (aq) + Cl (aq)

Strong acid

hydronium ion

weak acid

HCN (aq) H3O (aq) + CN (aq)

Arrhenius acid and base

Weak and strong bases

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

Conjugate acids and bases

Lewis acid

Lewis base
Acidic oxides

Basic oxides
Amphoteric reacts with both acids and bases

Amphipro7c both a proton donor and proton acceptor

!!!! !! !!" !
!= ! !
!!! !
 !! = !!!! !! !!" ! !

!! = !! !! !" ! !

!! = 1.0!!!10!! 1.0!!!10!! = 1.0!!!10!!" !

The pH scale

!" = −!"#!!! !! ≅ ! −!"# !! !! !

pOH = -log[OH-]

!!! !""# !" + !! ! ⇋ !! !! !" + !!! !!!! !" !

!!! !! !!"! !!!!

!= !
!!!! !""# !!! !

!! !! !"! !"!! !! !! !!
!! = !"! !""#
= !"
!!
 !"! !" !
!! = !
!!

!!! = −!"#!! !
Very weak acids have very large values of pKa due to very small values of Ka

Strong acids have weak conjugate bases

pKa + pKb = pKw

Molecular structure and acid strength

Enthalpy contribu9on

Acid strengths of binary acids correspond to

electron affini>es across the periodic table, but
correspond to bond strengths down the columns.
 !"#!$#%&'%("#!!"!!!
Percent deprotona,on = !!!100%!
!"#!$#%&'%("#!!"!!"

What is the pH of 0.080 M ace2c acidic? Ka of ace2c acid is 1.8 X 10-5

!!! !""# !" + !! ! ⇋ !! !! !" + !!! !!!! !" !

CH3COOH H3O- CH3CO2-

Ini,al concentra,on

Change in concentra,on

Equilibrium concentra,on

!! !! !"! !"!! !! !! !!
!! = = !!
!"! !""# !"
Salt solu,ons – not necessarily neutral

Conjugate acids of weak bases produce acidic solu,ons

Highly charged small ca,ons produce acidic solu,ons

Group 1 and 2 ca,ons are not acidic

Hydrogen aDached to an anion is usually not acidic

Conjugate bases of weak acids produce basic solu,ons

Conjugate bases of strong acids do not change pH

What is the pH of a 0.10 M ammonium nitrate solu,on?

!!!! !" + !! ! ⇌ !! !! + !!! !

Kb= 1.8 X 10-5

NH4+ H3O+ NH3

Ini,al concentra,on
Change in concentra,on
Equilibrium concentra,on
 Polyprotic acids and bases
can provide more than 1 p+

lose 1st p+ !! !!! !" + !! ! ! ⇌ !! !! !" + !"#!! !" ! Ka1 = 4.3 X 10-7

!
lose 2nd proton!"#! !" + !! ! ! ⇌ !! !! !" + !"!!! !" ! Ka2 = 5.6 X 10-11

Other than sulfuric acid, all polyprotic acids are weak, and the second
deprotonation event may be disregarded.
only common acid

Salts of polyprotic acids are amphiprotic

1
!" = !"!! + !"!! ! if: S>>Kw/Ka2 and S>>Ka1
2
s [ ] of the salt initially
Polyprotic acid concentrations

Determine the concentrations of the conjugate bases []= 0.10 M

!! !"! !" + !! ! ! ⇌ !! !! !" + !! !"!! !" !

H3PO4 H3O+ H2PO4-

Initial concentration .10 0 0

Change in concentration -x +x +x

Equilibrium concentration .1 + x +x +x

!!
!! !!
!!! = 7.6!!!10 = ≈ ! x = .028 x = 2.8 * 10^-2
0.10 − ! 0.10

[H2PO4-] = 2.4 X 10-2 mol/L

[H3PO4] = 0.08 mol/L

 !! !"!! !" + !! ! ! ⇌ !! !! !" + !!"!!! !" !

H2PO4- H3O+ HPO42-

Initial concentration 2.4 * 10^-2 2.4 * 10^-2 0

Change in concentration -x +x +x

Equilibrium concentration 2.4 * 10^-2 - x 2.4 * 10^-2 - x +x

2.4×10!! + ! ×!! 2.4×10!! ×!!

!!! = 6.2!!!10!! = ≈ !
2.4×10!! − ! 2.4×10!!

[HPO42-] = 6.2 X 10-8 mol/L

Effect of pH on composition
f(x) = fraction of species x in solution

!! !! !
! !! ! = !
!

!
!! !! !!!
! !! = !
!

!!! !!!
! !!! = !
!
Carbonic acid
Where:
H = [H3O+]2 + [H3O+]Ka1 + Ka1Ka2
pH = (1/2)(pKa1 +pKa2)
In very dilute solu/ons of strong acids and bases, autoprotolysis can not be ignored

For strong acids: (HCl) 2 species, 3 unknowns, 3 eqns

[H3O+] = [Cl-] + [OH-] [OH-] = [H3O+] - [Cl-] Charge balance #1

[Cl-] = [HCl]ini/al material balance #2

Kw = [H3O+] [OH-] autoprotolysis #3

[H3O+]2 - [HCl]ini/al[H3O+] - Kw = 0

not needed with

a strong acid
For weak acids:

[H3O+]3 + Ka[H3O+]2 – (Kw + Ka[HA]ini/al)[H3O+] - KaKw = 0

Buffer a solu'on in which the pH resists change
when small amounts of strong acids or bases are
added
Method to stabilize pH

An aqueous solu.on of either a weak acid and its

conjugate base, or a weak base and its conjugate
acid.
Counter ions are neutral

!!! !""# !" + !! ! ! ⇌ !! !! !" + !!! !!!! (!")!

if HCl added, more weak acid formed
if NaOH added, more salt formed

Provides both a source and a sink for protons

Acid buffer – weak acid and its conjugate base, pH<7

Basic buffer – weak base and its conjugate acid, pH>7

Calculate the pH of a buffer that is 0.15 M HNO2(aq) and 0.20 M NaNO2(aq)

!"!! !" + !! ! ! ⇌ !! !! !" + !!!! (!")! Ka = 4.3 X 10-4

!!!! [!! !! ] !
[!!!! ]
!! = ! !! ! = !! × ! !
[!!!! ] [!!! ]
Addi.on of strong acid or base to a buffer – changes the ra'o of weak acid to
conjugate base, or of weak base to conjugate acid.

!"!! !" + !! ! ! ⇌ !! !! !" + !!!! (!")!

!
[!!!! ]
!! ! = !! × ! !
[!!! ]
So addition of acid or base does not directly change [H3O+]

If equal number of moles of acid and conjugate base (or weak base and
conjugate acid)

pH = pKa

This is the normal way to make a buffer

Reality does not always equal theory: ac.vity is not always the same as molarity
a = M only in dilute solutions (no higher concentrations)

Effec.ve molari.es
increase in [ ] reduces effectiveness more ion interactions

Henderson-Hasselbalch equa.on:

[!"#$]!"!#!$%
!" = !"! + log! !
[!"#$]!"!#!$%

Assumes:
1. The concentra.on of acid or base does not change much in water
2. The ac.vity is equal to the molarity
3. Autoprotolysis is not significant
Buffer systems are most effec.ve when the pH is within 1 of the pKa
No more than a 10x excess of either component

!! !"! + !! ! ⇌ !! !! + !"#!! ! H2CO3 : HCO3- 1:20 in blood

Respiratory acidosis low pH due to increased [CO2]

from decreased respira'on

Metabolic acidosis low pH due to difficul'es

removing acidic metabolic byproducts (lac'c acid)

Respiratory alkalosis high pH due to excessive

respira'on (hyperven'la'ng)

Metabolic alkalosis high pH due to illness or

poisoning
Titra&ons – adding one solu&on to another

Titrant- the solu&on that is added

Analyte – substance added to

Stoichiometric point – when the number of hydronium ions equals

the number of hydroxide ions

Strong acid / strong base

Strong acid / weak base
Stoichiometric point is not at pH 7
Strong base / weak acid

What is the pH at the stoichiometric point for 25 mL of 0.010 M

hypochlorous acid HClO(aq) &trated with 0.020 M KOH(aq)?

!"!" !" + !"#(!") → ! ! !"!! (!") + !! !(!)!

!"#$ !" + !! !(!) ⇌ !"!! (!") + !! !! (!")!

Ka= 3.0 X 10-8

 ClO- HClO -OH

Ini&al
change
final
pKa of a weak acid can be determined by adding half of the amount of strong base
needed for neutraliza&on. The pH at that point is the pKa of the weak acid.

Acid / base indicators change color with pH, as the protonated form has a different
shape than the non-protonated form, color change typically occurs from 1 pH unit
below pKIn to 1 pK unit above pKIn.

End point is when pH = pKIn

The indicator used should

have its end point close to the
stoichiometric point of the
system, but with strong acids
and bases this is not
necessary.
Polypro&c acids behave as separate weak
acids, producing a &tra&on curve with
mul&ple stoichiometric points.

The solubility product - Ksp

!"! (!"! )! (!) ⇌ 3!!"!! (!") + 2!!"!!! (!")!

!
!!" = !!"!! !
!!"!!! ! !!" = !"!! !
!"!!! !
!

Generally only good for low solubility salts

Dissocia&on is not always complete
s = molar solubility – the molar concentra3on of a saturated solu3on

The solubility product is the equilibrium constant for the ions of a dissolved salt
and the dissolved salt
Common – ion effect by adding more of an ion that appears on the right hand side
of an equilibrium of a weakly soluble salt, the weakly soluble salt can be
precipitated out of solu;on as its equilibrium (insoluble on the le=, soluble on the
right) is driven to the le= by Le Chatelier’s principle.

!"#(!) ⇌ !"! (!") + ! ! (!")!

Adding NaI increases the amount of I- in solu3on, driving the equilibrium to the le@,
crea3ng more solid material (precipita3ng out the copper iodide).

Like with equilibriums, there is a Qsp

When Qsp > Ksp precipita3on will occur

Does silver chloride precipitate when 200 mL of 1.0 X 10-4 M silver nitrate and 900 mL of
1.0 X10-6 M potassium chloride are mixed, assuming complete dissociaCon?

! ! Ksp for silver chloride is 1.6 X 10-10

!"#$(!) ⇌ !" (!") + !" (!")!
Ksp = [Ag+][Cl-]
It can be possible to selecCvely precipitate out certain caCons by adding anions
that form less soluble salts

!"!"! ⇌ !"!! (!") + !"!!! (!")! Ksp = 8.1 X 10-9

!"!"! ⇌ !"!! (!") + !"!!! (!")! Ksp = 8.7 X 10-9

!"! ⇌ !"! (!") + ! ! (!")! Ksp= 0.907 (*)

!"!! ⇌ !"!! (!") + 2! ! (!")! Ksp = 1.7 X 10-6

!"!! ⇌ !"!! (!") + 2! ! (!")! Ksp = 4.0 X 10-11

 Precipitates can also be dissolved by removing one of the salts from soluCon

Removing the anion with an acid

!"(!!)! (!) ⇌ !" !! (!") + 3!!" ! (!")!

Removing the anion by conversion into a gas

!"!"! (!) ⇌ !"!! (!") + !"!!! (!")!

Removing the anion by oxidaCon

!"#(!) ⇌ !"!! (!") + ! !! (!")!

Removing the caCon by formaCon of a complex ion

!"! (!") + 2!! !!!! (!") ⇌ !" !! !! !!

! (!") !
What is the molar solubility of copper (II) sulfide in 1.2 M aqueous ammonia?

!"#(!) ⇌ !"!! (!") + ! !! (!")! Ksp = 1.3 X 10-36

!!
!"!! (!") + 4!"! (!") ⇌ !" !"! ! (!")! Kf = 1.2 X 1013

!!
!"#(!) + 4!"! (!") ⇌ !" !"! ! (!") + ! !! (!")!
Redox Reac)ons (REDuc)on and OXida)on)

LEO and GER

Half reac)on is either the oxida)on or the reduc)on part of the reac)on considered
in isola)on.

!"(!) + 2!!"! (!") → !"!! (!") + 2!!"(!)!

Has two half reac)ons:

!"(!) → !"!! (!") + 2!! ! !

electrons in transit
!"! (!") + ! ! → !"(!)!

Redox couple = Ox/Red Zn2+/Zn and Ag+/Ag

Balance the reac)on of copper with dilute nitric acid to form copper(II) nitrate and nitric
oxide gas.

First, write the skeletal reac)on.

!" ! + !"!! !" → !" !!! ! !" + !" ! !

Next, iden)fy what is being oxidized and what is being reduced

!"(!) + !! !!! ! (!") → !"!! (!!! ! )! (!") + !"(!)!

!!!! ! !!! ! !!!! !

!!!! !
(! !! )
(! !! ) → ! ! !
! → !
!
!"! → !"!! !

Balance the elements other than oxygen and hydrogen

As this is an acid solu)on, balance the oxygen by adding H2O to both sides

!!!! → !!! !!!! → !! + 2!!! !!

! goes to
!" → !"!! ! !" → !"!! !

and balance the hydrogen by using H+.

!!!! + 4!!! → !" + 2!!! !!

!
!" → !"!! !
(If it had been a basic solu)on, the oxygen would be balanced using –OH and the
hydrogen would be balanced using H2O.)

Next, balance the charges by adding electrons to the leR for reduc)ons and the right for
oxida)ons.
!!!! + 4!!! + 3!! ! → !" + 2!!! !!
!
!" → !"!! + 2!! ! !
If necessary, mul)ply through the half reac)ons to give equal numbers of electrons on
the leR and right side.
2!!!!! + 8!!! + 6!! ! → 2!" + 4!!! !! by 2

3!!" → 3!!"!! + 6!! ! ! by 3

Finally, add the reac)ons together and cancel terms that are same on both sides.

2!!!!! + 8!! ! + 6!! ! + 3!!" → 2!" + 4!!! ! + 3!!"!! + 6!! ! !

!
3!!"(!) + 2!!"!! (!") + 8!! ! (!") → 3!!"!! (!") + 2!!"(!) + 4!!! !!

Double check to be sure the atoms and charges on each side match
Electrochemical cell / a device in which an electric current either results in a non -
spontaneous reac5on or a spontaneous reac5on produces an electric current.

Galvanic Cell / an electrochemical cell in which a spontaneous reac5on is used to

generate an electric current.

Ba<ery / galvanic cells joined in series

Two metallic electrodes that make electric contact with

the cell but not with each other. The species being oxidized
releases electrons which flow to the species being reduced.
This electron flow can do work.

Anode / where oxida5on takes place

Cathode / where reduc5on takes place
 The Daniell Cell

!"(!) + !"!! → !"!! (!") + !"(!)!

!"(!) + !"!! !"!!! (!") → !"!! !"!!! (!") + !"(!)!

As Cu2+ is reduced to Cu0, the sulfate ions are sAll

around, but their charge is no longer balanced by the
copper, and so a net negaAve charge starts to form.
Likewise, as the Zn is oxidized to Zn2+, there are not
enough sulfate ions around to balance the posiAve
charge on the zinc, and so a net posiAve charge builds
up. The porous walls of the “pot” allow the excess
sulfate ions around the copper cathode to flow to the
posiAve charge forming at the zinc anode, and in this
way the electrolyte carries charge to complete the
circuit.

A system consis5ng of a metal conductor and electrolyte is called the electrode or half-cell.
Volt (V) is the SI unit for the for electric poten5al (and poten5al difference)

J = C x V one coulomb falling through one volt poten5al difference generates

one joule of energy

A volt is analogous to the gravita5onal poten5al.

Electrical work is an example of non-expansion work, meaning the maximum

amount of work is equal to ΔG.

ΔG = we

we = (total charge) x (poten5al difference) = (-neNA) x E

Faraday’s constant, F = (eNA) = 9.6458 x 104 C/mol e-

ΔG = we = -nFE

ΔGr = -nrFE
 ΔGr = -nrFE

So if E is posi5ve, ΔG is nega5ve, and the reac5on will be spontaneous.

This equa5on represents the system ac5ng reversibly (called the cell poten5al, Ecell, or
electromo5ve force, emf), meaning actual systems will produce a smaller poten5al
difference, or voltage (or pushing power), than predicted by this equa5on.

ΔGr = -nrFEcello Ecello = standard cell poten5al

One important note: mul5plying through a reac5on by some factor does not change
the value of Ecello but does change ΔGo by that factor.
Cell nota5on
For the Daniell cell:

Zn(s)|Zn2+(aq)|Cu2+|Cu(s)
where the ver5cal line represents an interface

In order to avoid the direct interacAon of ions, such as the

copper sulfate and zinc sulfate, a salt bridge can be used.

For a salt bridge:

Zn(s)|Zn2+(aq)||Cu2+(aq)|Cu(s)

For a solu5on of manganese (II) with a manganese wire as the le_ electrode, a salt
bridge, and a copper (II) copper(I) electrode with a pla5num wire, the cell nota5on is:

Mn(s)|Mn2+||Cu2+(aq),Cu+(aq)|Pt(s)
 Zn(s)|Zn2+(aq)||Cu2+(aq)|Cu(s) Ecell = +1.10 V

electrons flow from the anode on the le_ to the cathode on the right

Cu(s)|Cu2+(aq)||Zn2+(aq) Zn(s) Ecell = -1.10 V

By convenAon, we write the oxidaAon on the leM hand side, and the reducAon on the
right hand side. That means the anode is on the leM, and the cathode is on the right.

Anode is nega5ve - t
Ca hode is posi5ve +
Electrons flow to the posi5ve charge, so the anode is supplying the electrons that flow
to the posi5ve cathode. Because oxida5on is LEO (loss of electrons oxida5on),
oxida5on occurs at the anode to provide the electrons that move to the cathode.
Because reduc5on is GER (gain electrons reduc5on) the cathode gets the electrons
supplied by the oxida5on at the anode.
The strongest oxidizing agents are at the top left of the standard potential table, and the
strongest reducing agents are at the bottom right of table.

If Ecello > 0, then K > 1 for that cell reaction

!
−!"#$% = ∆!!! =-!! !"!"## !

!
!! !"!"## = !"#$% !

!! !" !
!"# = !
!"

It is possible to predict the standard cell potential and calculate the reaction Gibbs
free energy for galvanic cells.
 What is the value of Ecello and DGo for the reaction:

3!!"(!) + 2!!" !! (!") → 3!!"!! (!") + 2!!"(!)!

!" !! (!") + 3!! ! → !"(!)! Eo = +0.20 V a reduction, this is the cathode

an oxidation (reverse of the

!"!! (!") + 2!! ! → !"(!)! Eo = -0.76 V
reduction written) this is the anode

Ecello = Erighto -Elefto Ecello = +0.20 V –(-0.76 V) = +0.97 V

By convention, reduction on right. n = number of electrons transferred,

for this example, there were 6
electrons transferred.

DGro = -nFEo = -6(9.6485 x 104 J/V mol)(+0.96 V) = -5.6 x 102 kJ/mol

The Nernst Equation concentration dependence of cell potential

∆!! = ∆!!! + !"#$%!

!
−!! !"!"## = −!! !"!"## + !"#$%!

at 298.15 K:
Concentration cell two electrodes differ only in the concentration of their reagents

Ion selective electrode sensitive to the concentration of a specific ion

1. Thin glass doped with oxides of other metals, such as Na

2. Internal electrode, often calomel

!"! !"! (!) + 2!! ! → 2!!"(!) + 2!!" ! (!")!

3. pH= 7 buffered 0.1 M KCl

4. Depending on the system, some salt can precipitate

5. Reference electrode, often calomel as well

 6. Internal reference solution, often 0.1 M KCl

7. Connection with the external solution to be studied

8. Non-conductive structure of the electrode

Glass electrode||Reference Solution||Test solution||Glass electrode

Hg2Cl2|Hg|KCl||10-7 M H+||glass membrane||solution||junction||KCl|Hg|Hg2Cl2

! !" !
!"
!!"## = !!"## − !"[!" ] − !"[!! ]!
! !

Not linear at very high or low pH.

Stored in dilute aqueous acid to prevent drying.
Corrosion is an electrochemical process

2!!! !(!) + 2!! ! → !! (!) + 2!!"! ! Eo = -0.83 V

!" !! (!") + 2!! ! → !"(!)! Eo = -0.44 V

!! (!) + 4!!! (!") + 4!! ! → 2!!! !(!)! Eo = +1.23 V

Galvanize a thin film of zinc on the surface of the iron

Protective oxide

Sacrificial anode a block of more strongly reducing

metal connected to the metal to be protected
Electrolysis the process of driving a non-spontaneous reac3on by the use of an
electric current

Electroly,c cells typically have both electrodes in the same electrolyte solu,ons and
are far from standard concentra,ons.

A poten3al must be supplied at least as great as the

poten3al that would be expected from the reverse
reac3on. The excess poten3al generally applied is the
overpoten3al.

Faraday’s Law of electrolysis: The amount of product

formed or reactant consumed by an electric current is
stoichiometrically equivalent to the amount of
electrons supplied.
 Quan,ty of electricity passed through a cell is:

Charge (C) = current (A) x ,me (s)

Q = I x t

Remember F = magnitude of charge per mole of electrons

! !"
!= = !
! !

What amount (in moles) of Al(s) can be produced from Al2O3 if 5.0 mole of e- are supplied?

!" !! + 3!! ! → 2!!" ! !

1!!"#!!"
!
!"#$%&!!"!!" = (5!!"#!! )× !
= 1.7!!"#!!" !
3!!"#!!
BaMeries

Zn(s)|ZnCl2(aq),NH4Cl(aq)|MnO(OH)(s)|MnO2(s)|graphite

Primary cells are galvanic cells.

Secondary cells must be charged before using and can normally be recharged many ,mes.