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H+(aq) + A(aq)
Weak Bases
Weak bases remove protons from substances.
There is an equilibrium between the base and the resulting ions:
Weak base + H2O(l)
NH3(aq) + H2O(l)
NH4+(aq) + OH(aq).
[NH ][OH ] K
+
[NH 3]
H3O+(aq) + A(aq):
Calculating Ka from pH
In order to find the value of the Ka, we need to know all of the
equilibrium concentrations.
The pH gives the equilibrium concentration of H+.
Thus, to find Ka, we use the pH to find the equilibrium
concentration of H+ and then the stoichiometric coefficients of the
balanced equation to help us determine the equilibrium
concentrations of the other species.
We then substitute these equilibrium concentrations into the
equilibrium constant expression and solve for Ka.
Using Ka to Calculate pH
[H ]
+ equilibrium
% ionization = 100
[HA]initial
Weak acids are only partially ionized.
Percent ionization is another way to assess acid strength.
For the reaction HA(aq)
H+(aq) + A(aq)
Acid-Base Titrations
Consider adding a strong base (e.g., NaOH) to a solution of a strong acid (e.g.,
HCl).
We can divide the titration curve into four regions.
1. Initial pH (before any base is added).
The pH is determined by the concentration of the strong acid solution.
Therefore, pH < 7.
2. Between the initial pH and the equivalence point (see next slide).
When base is added, before the equivalence point, the pH is given by the
amount of strong acid in excess.
Therefore, pH < 7.
3. At the equivalence point.
The amount of base added is stoichiometrically equivalent to the amount
of acid originally present.
Therefore, the pH is determined by the hydrolysis of the salt in solution.
Therefore, pH = 7.
4. After the equivalence point.
The pH is determined by the excess base in the solution.
Therefore, pH > 7.
How can we analyze the titration (i.e., how will we know when we are at the
equivalence point)?
The shape of a strong basestrong acid titration curve is very similar to a strong
acidstrong base titration curve.
Initially, the strong base is in excess, so the pH > 7.
As acid is added, the pH decreases but is still greater than 7.
At the equivalence point, the pH is given by hydrolysis of the salt solution (
i.e., pH = 7).
After the equivalence point, the pH is given by the strong acid in excess, so
the pH < 7.
Weak AcidStrong Base Titration
Consider the titration of acetic acid, HC2H3O2, with NaOH.
Again, we divide the titration into four general regions:
1. Before any base is added :
The solution contains only weak acid.
Therefore, pH is given by the equilibrium calculation.
2. Between the initial pH and the equivalence point.
As strong base is added it consumes a stoichiometric quantity of weak
acid:
HC2H3O2(aq) + OH(aq)
C2H3O2(aq) + H2O(l)
The pH curve for a weak acidstrong base differs significantly from that of a
strong acidstrong base titration.
For a strong acidstrong base titration:
The pH begins at less than 7 and gradually increases as base is added.
Near the equivalence point, the pH increases dramatically.
For a weak acidstrong base titration:
The initial pH rise is steeper than that for a strong acidstrong base
titration.
However, then there is a leveling off due to buffer effects.
The inflection point is not as steep for a weak acidstrong base titration.
The shape of the two curves after the equivalence point is the same because
pH is determined by the strong base in excess.
The pH values at the equivalence points differ also:
The pH = 7.00 for the strong acidstrong base equivalence point.
The pH >7.00 for the weak acidstrong base equivalence point.
How to choose indicators: we select the appropriate indicator based upon the pH
of the salt solution formed at the equivalence point.
The pH curve for the titration of a weak base with a strong acid also differs
significantly from that of a strong base-strong acid titration.
Consider the titration of NH3 with HCl.
The equivalence point occurs at pH 5.28 so phenolphthalein should
not be used for this titration.
The color change for methyl red occurs in the pH range from 4.2 to 6.0
so it is a good indicator to use for this titration.
Salts derived from a weak acid and a weak base can be either acidic or basic.
Equilibrium rules apply!
We need to compare Ka and Kb for the hydrolysis of the anion and the
cation.
For example, consider NH4CN.
Both ions undergo significant hydrolysis.
Is the salt solution acidic or basic?
The Ka of NH4+ is smaller than the Kb of CN, so the solution should be
basic.
Buffered Solutions
A buffered solution or buffer is a solution that resists a change in pH upon addition of
small amounts of acid or base.
Composition and Action of Buffered Solutions
A buffer consists of a mixture of a weak acid (HX) and its conjugate base (X ).
Thus a buffer contains both:
Buffer capacity is the amount of acid or base that can be neutralized by the
buffer before there is a significant change in pH.
Buffer capacity depends on the concentrations of the components of the buffer.
The greater the concentrations of the conjugate acid-base pair, the greater the
buffer capacity.
The pH of the buffer is related to the Ka and on the relative concentrations of the
acid and base.
We can derive an equation that shows the relationship between conjugate
acidbase concentrations, pH, and the Ka.
By definition:
Ka =
Rearranging, we get:
[H ]=K [HA
+
[A ]
If we take the negative log of each side of the equation we get:
log[H+ ] =log Ka log
By definition:
pH = pKa log
[ ]
A
base ]
[
a
pH = pKa + log
pK
log
=
+
HA
[ ]
[acid]
HX + OH X + H2O
By knowing how much H3O+ or OH was added, we know how much
HX or X is formed.
This is the stoichiometric calculation.
From the concentrations of HX and X (note the change in volume of
solution) we can calculate the pH from the Henderson-Hasselbalch
equation:
pH = pKa + log
Determination of acidity
Salt Solution
Hydrolysis reaction
pH
Explanation
0.1M NH4OAc
~7
NR
0.1M NaOAc
>7
0.1M NH4Cl
<7
0.1M NaHCO3
>7
0.1M NaCl
0.1M Na2CO3
>7
Color with
Phenolphthalein
0.1M HOAc
Red
Colorless
Red
Colorless
0.1M NH4OH
Yellow
Red
Yellow
Red
Solution
Buffer solutions
+ HCl
+ NaOH
+ HCl
+ NaOH
Weak acid
HOAc
Red
Colorless
HOAc
Yellow
Pink
Red
Colorless
HOAc + NaOAc
Red / yellowish
red
Colorless / light
pink
Weak base
NH4OH
Yellow
Colorless
NH4OH
Red
Pink
Yellow / Reddish
yellow
Light pink
NH4OH + NH4Cl
Yellow
Pink
Answers to questions
1.
A little bit because the presence of the salt lowered the concentration of the
H+ or the OH- due to common ion effect.
2.
3.
Buffer solutions are mixtures of solutions of weak electrolytes and the salts
of their conjugate ions. They resist pH changes as explained in #2.
4.
of 0.01mole HCl:
pH = -log(1.75 10-5) + log (0.05L 0.1M) 0.01mole) (0.05L 0.1 M )+ 0.01mole ))
Oxidation-Reduction Reactions
Chemical reactions in which the oxidation state of one or more substances
changes are called oxidation-reduction reactions (redox reactions).
Recall: OILRIG
Oxidation involves loss of electrons (OIL).
Reduction involves gain of electrons (RIG).
Electrochemistry is the branch of chemistry that deals with relationships
between electricity and chemical reactions.
Consider the spontaneous reaction that occurs when Zn is added to
HCl.
2+
Zn(s) + 2H+(aq)
Zn (aq) + H2(g) The
oxidation numbers of Zn and H+ have changed.
The oxidation number of Zn has increased from 0 to +2.
The oxidation number of H has decreased from +1 to 0.
Balancing Oxidation-Reduction
Equations
Recall the law of conservation of mass: the amount of each element
present at the beginning of the reaction must be present at the end.
Conservation of charge: electrons are not lost in a chemical reaction.
Some redox equations may be easily balanced by inspection.
However, for many redox reactions, we need to look carefully at the
transfer of electrons.
Sn4+(aq) + 2Fe2+(aq)
Sn4+(aq) +2e
2Fe2+(aq)
C2O42(aq)
Balance each half-reaction:
Mn2+(aq)
CO2(g)
C2O42(aq)
Mn2+(aq)
2CO2(g)
MnO4(aq)
(aq) 2CO2(g)
Mn2+(aq) + 4H2O(l)
C2O42(aq) 2CO2(g)
Finish by balancing charge by adding electrons.
This is an easy place to make an error!
For the permanganate half-reaction, note that there is a
charge of 7+ on the left and 2+ on the right.
Therefore, 5 electrons need to be added to the left:
5e + 8H+(aq) + MnO4(aq)
Mn2+(aq) + 4H2O(l)
C2O42(aq)
2CO2(g) + 2e
2Mn2+(aq) + 8H2O(l)
10CO2(g) + 10e
Voltaic Cells
The energy released in a spontaneous redox reaction may be used to
perform electrical work.
Voltaic or galvanic cells are devices in which electron transfer occurs
via an external circuit.
Voltaic cells utilize spontaneous reactions.
If a strip of Zn is placed in a solution of CuSO4, Cu is deposited on the Zn
and the Zn dissolves by forming Zn2+.
2+
Zn(s) + Cu2+(aq)
Zn (aq) + Cu(s)
Zn is spontaneously oxidized to Zn2+ by Cu2+.
The Cu2+ is spontaneously reduced to Cu0 by Zn.
The entire process is spontaneous.
This voltaic cell consists of:
An oxidation half-reaction:
Zn(s)
Zn2+(aq) + 2e
Cu(s)
Cell EMF
The flow of electrons from anode to cathode is spontaneous.
What is the driving force?
Electrons flow from anode to cathode because the cathode has a lower
electrical potential energy than the anode.
Potential difference: difference in electrical potential.
The potential difference is measured in volts.
One volt (V) is the potential difference required to impart one joule (
J) of energy to a charge of one coulomb (C ):
1V = 1 J / C
Electromotive force (emf) is the force required to push electrons
through the external circuit.
Cell potential: Ecell is the emf of a cell.
This is known as the cell voltage.
Ecell > 0 for a spontaneous reaction.
Zn(s) + Cu2+(aq)
Zn2+(aq) + Cu(s)
Ecell = +1.10 V.
Standard Reduction Potentials
We can conveniently tabulate electrochemical data.
Standard reduction potentials, Ered, are measured relative to a standard.
The emf of a cell can be calculated from standard reduction potentials:
Ecell = Ered(cathode) - Ered( anode )
We use the following half-reaction as our standard:
2H+(aq, 1M) + 2e
Zn2+(aq) + 2e
Zn2+(aq, 1 M) + 2e
Reactions with Ered > 0 are spontaneous reductions relative to the SHE.
Reactions with Ered < 0 are spontaneous oxidations relative to the SHE.
The larger the difference between Ered values, the larger the Ecell.
The more positive the value of Ered, the greater the driving force for
reduction.
Oxidizing and Reducing Agents
Consider a table of standard reduction potentials.
Ni2+(aq) + 2Ag(s)
C J
F = 96,500
Since n and F are positive, if G < 0, then E > 0, and the reaction will
be spontaneous.
Or
E = E
E = E
RT
ln Q
nF
2. 303 RT
log Q
nF
0.0592
E = E log Q
n
Example: If we have the reaction:
Zn(s) + Cu2+(aq)
Zn2+(aq) + Cu(s)
0.
Ecell = 1.10V = 1.16V
Cell EMF and Chemical Equilibrium
A system is at equilibrium when G = 0.
From the Nernst equation, at equilibrium;
nE
logK =
.0592
Thus, if we know the cell emf, we can calculate the equilibrium
constant.
Experiment 8: Electrochemistry