Beruflich Dokumente
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INTRODUCTORY UNIVERSITY
CHEMISTRY II
¾ This course focuses upon many of the
essential concepts in physical
chemistry, which is the branch of
chemistry concerned with the application of
the laws of physics to chemical phenomena.
aA + bB cC + dD
Kc = [C]c×[D]d
[A]a ×[B]b
PCc × PD d
KP = ,
PA a
× PB b
N2O4(g) 2NO2(g)
2
where Kc = [NO 2 ]
[N 2O 4 ]
Calculate Kc for the two following experiments (assume T is the same
for both experiments)
Experiment 1
Initial Concentrations Equilibrium Concentrations
[N2O4] = 1.0 M [N2O4] = 0.80 M
[NO2] = 0.0 M [NO2] = 0.40 M
Gaseous Equilibria
¾ When the system under study involves only gases, it is customary to
use equilibrium partial pressures, which are proportional to
concentrations, in place of equilibrium concentrations (pressures of
gaseous mixtures are easily measured).
N2(g) + 3H2(g)
2NH3(g)
[NH3 ] 2 ( PNH3 ) 2
Kc = and KP = 3
(preferred)
[N 2 ][H 2 ]3
( PN2 )(PH 2 )
¾ The numerical values for KP and Kc are related by the expression
Δn g
K P = K c (RT)
L • atm
R = 0.08206 ; T = Temperature in Kelvins
moles • K
Note: When ∆ng = 0, KP = Kc
n
K new = ( K original )
Heterogeneous Equilibria
CaCO3(s)
CaO(s) + CO2(g)
and KP = PCO2
¾ Note that the equilibrium concentration of CO2 is not
affected by the amount of CaO and CaCO3 present.
However, at least a small quantity of both of these solids
must be present. Without both solids being in contact with
gaseous CO2, the reaction cannot occur and, clearly, the
system, as a result, will not be at equilibrium.
e.g. CH3COOH(aq) + CH3OH(aq) CH3COOCH3(aq) + H2O(l)
has Kc = 2.0 M-1 at 25oC.
Thus, the equilibrium mixture at 25oC contains a “dog’s
breakfast” of roughly equal amounts of CH3COOH(aq) ,
CH3OH(aq) and CH3COOCH3(aq).
Effect of a Catalyst
CO(g) + 2H2(g)
CH3OH(g) KP = 10.5 atm-2
at 500 K
Increase total gas pressure To the side of the equation with fewer moles
by decreasing volume of gas (to decrease the pressure)
Decrease total gas pressure To the side of the equation with more moles
by increasing volume of gas (to increase the pressure)
Sample Problem:
For the reaction
N2(g) + 3H2(g) 2NH (g)
3 ∆Ho = -92 kJ/mol rxn
at equilibrium in a closed vessel at 773 K and 350 atm pressure, in
which direction will the equilibrium shift in response to each of the
following changes in conditions ?
a) Remove some NH3
b) Add some more N2
c) Decrease the volume of the system while keeping T constant
d) Add a catalyst
e) Increase the total pressure by adding some He gas
f) Increase the temperature
How to Solve Equilibrium Problems: The ICE Table Method
6. If all of the (Ci/K) ratios for those species with non-zero initial
concentrations/partial pressures are greater than 1000, then the
reaction is a Small K problem. In situations where K is small, we
can employ what is called an heuristic strategy, which involves
making certain legitimate approximations that make the solution to
the problem more simple. One can avoid solving quadratic
equations or higher order polynomials by ignoring the amount nx
that is added to or subtracted from the concentration or partial
pressure of a reactant or product if the amount nx is less than 5%
of the reactant/ product concentration or partial pressure to which it
is to be added or from which it is to subtracted (This is called the
5% rule). The amount nx will be less than 5% of the initial reactant/
product concentration or partial pressure when the ratio Ci/K
>1000.
7. If all of the (Ci/K) ratios for those species with non-zero initial
concentrations/partial pressures are less than 0.001, then the reaction is
a Large K problem. In situations where K is large, the algebraic
determination of the equilibrium concentrations is made much simpler if
we first take the reaction 100% to completion and then back it up a little
bit to get to the state of equilibrium. It is during the backing-up step that
we introduce the unknown x. Effectively, what we accomplish by first
taking the reaction 100 % to completion in the direction for which K is
large is to convert the system into one that can be solved via the Small K
approach. By introducing x in the back-up step, we ensure that it will be
negligible with respect to the concentration or partial pressure of at least
one species in the balanced equation, which will cause the order of
the polynomial to decrease when we apply the 5% rule. (Final note:
whenever the Ci/K ratio for a reactant or product is greater than 1000,
any associated nx term can be ignored).
9. Finally, if you invoke the 5% rule, you must make certain that the
assumption you made does not introduce more than 5 % error. If the
error created by the assumption exceeds 5 %, the approximation cannot
be made and the complete polynomial must be solved.
The Method of Successive Approximations
¾ Acids and bases have widespread use in our society and they play essential
roles in the chemistry of living systems.
Arrhenius Definition
This is a somewhat limited definition as it allows for only one kind of base
(viz. OH-(aq)) and it is restricted to aqueous solution.
¾ They act as Bronsted bases towards stronger acids and Bronsted acids
towards stronger bases.
e.g. H2O is an amphoteric substance
¾ The strengths of acids and bases are defined by the positions of their
dissociation reactions with water (i.e. through their Ka and Kb values,
respectively).
Acid Hydrolysis
[H 3O + ][A − ]
Ka = ; [H 2 O](pure liquid) = 55.5 M( Blended into K a )
[HA]
Base Hydrolysis
[BH + ][OH − ]
Kb = ; [H 2 O](pure liquid) = 55.5 M( Blended into K b )
[B :]
For strong acids, the hydrolysis equilibrium lies far to the right
(Ka >>1), while
For weak acids, the hydrolysis equilibrium lies far to the left (Ka<< 1).
Similarly,
For strong bases, the hydrolysis equilibrium lies far to the right
(Kb >>1), while
For weak bases, the hydrolysis equilibrium lies far to the left (Kb<< 1).
¾ e.g. CH3COO-(aq) is weak base (meaning much weaker
than OH-(aq)), as indicated by its small Kb value
(Kb CH3COO-(aq) = 5.68 × 10-10 M).
¾ When they are dissolved in water, bases produce hydroxide ion via
deprotonation of water molecules.
¾ The weak base ammonia, for instance, can produce hydroxide ion
via nucleophilic attack of its lone pair on one the polarized O-H
bonds in an adjacent water molecule (vide infra):
Acid-Base Behaviour and Chemical Structure
¾ Next we will consider what factors influence the strength of acids.
Binary Acid
¾ Binary acids are the simplest acids known. They contain hydrogen along with
a non-metal element; H2Se and HCl are examples.
¾ Binary acid strength increases from left to right across a period and from top
to bottom within a vertical group (vide infra):
¾ In general, the H-X bond strength is the most important determinant of acid strength.
¾ The more polar the H-X bond, the stronger the acid and the weaker the H-X bond, the
stronger the acid.
¾ As X becomes more electronegative, the H-X bond becomes more polar and hence
more susceptible to cleavage.
¾ Thus, the acidity of binary acids formed from elements in the same period increases
from left to right.
¾ For instance the binary acids formed from elements in the latter half of the second row
follow trend
¾ The strength of an H-X bond tends to decrease as the element X
increases in size.
¾ Thus, H-X bond strength decreases and the acidity of the binary acid
increases down a given group.
Oxyacids
Consider, for instance, the trend for the hypohalous acids below:
e.g. Placing more and more oxygens on the Cl atom of HOCl leads to
a steady increase in acidity
Levelling Effect
¾ All acids stronger than H3O+(aq)
(Ka = 1.8 × 10-3 M) ionize to ca. 100% in water and appear equally
strong (i.e. the strongest acid that can exist in water is H3O+(aq)
because all stronger acids protonate water virtually quantitatively).
¾ Therefore, strong bases are leveled to the strength of OH- and thus
the strongest base that can exist in water is hydroxide ion.
K archetype × [H 2 O]2 = K w
pH + pOH = 14.000
Acidic Solutions:
−7 −7
[H3O+] > 1.00 × 10 M ; [OH-] < 1.00 × 10 M ;
There are more protons than hydroxide ions in these solutions
Thus, pH < 7.000 while pOH > 7.000
Basic Solutions:
−7 −7
[H3O+] < 1.00 × 10 M ; [OH-] > 1.00 × 10 M ;
There are more hydroxide ions than protons in these solutions
Thus, pH > 7.000 while pOH < 7.000
pH of a Solution of a Strong Acid or Strong Base
Sample Problem:
Calculate the [OH-], [H3O+], pH and pOH for a solution prepared by
dissolving 0.60 g of Ca(OH)2 in pure water and making it up to
the1.00 L mark in a volumetric flask at 25oC.
Relationship between Ka and Kb for a Conjugate Acid-Base Pair in H2O
Acid Hydrolysis:
[H 3O + ][A - ]
HA(aq) + H2O(l) H3O+(aq) + A-(aq) Ka =
[HA]
+
Base Hydrolysis
[OH - ][HA]
A-(aq) + H2O(l) HA(aq) + OH-(aq) Kb =
[A - ]
___________________________________________________________
Net: + - -
[H O ][A ] [OH ][HA]
2H2O(l) H3O+(aq) + OH-(aq) K a × K b = 3
×
[HA] [A - ]
Or
Ka × K b = K w
This equation quantifies the principle that a strong acid has a weak
conjugate base and vice versa (i.e. If the Kb for the base is large, then
the Ka for the conjugate acid will be small). Moreover, the fact that the
product of the two hydrolysis equilibrium constants is equal to the self-
ionization constant for water tells us that all acid-base reactions that
occur in water are intimately linked to the self ionization reaction for
water itself.
Taking log10 of both sides of the expression above we
obtain
¾ For any acid-base reaction, the equilibrium will always favour the side
with the weaker acid and the weaker base.
Sample Problem:
Write the equation for the reaction of HSO4-(aq) with HS-(aq) and
determine if the equilibrium position favours reactants or products.
(Note: If the reactants are amphoteric, the species with the larger Ka
will act as an acid).
Acid-Base Properties of Salts: Neutral Solutions, Cation Hydrolysis and
Anion Hydrolysis
¾ Certain ions, when released, will react with water (i.e. hydrolyze) to give
acidic or basic solutions, depending on the natures of the anion and
cation.
¾ Conjugate bases of strong acids (e.g. Cl-, Br-, I-, NO3-, ClO4-) do not
hydrolyze to a measurable extent.Thus, these ions have no detectable
effect on the pH.
[HA][OH − ]
A-(aq) + H2O(l) HA(aq) + OH-(aq) Kb =
[A - ]
[BH + ]
Protons outnumber hydroxide ions in the solution at equilibrium; thus
pH < 7.00
Sample Problem:
For aqueous solutions of the following two salts, classify each of the ions
as acidic, basic or neutral. Write a net ionic equation for any hydrolysis
reaction, indicate the value of the Ka or Kb as appropriate and state
whether the resulting solution will be acidic, basic or neutral.
a) KBr
b) NH4CH3COO
Calculating Equilibrium Constants for Acid-Base Reactions in Aqueous
Solution
Solution:
First step: Write down the major species in the mixture
In this case, the two major species are H2O(l) and HOCl(aq)
(Please note, however, that if the Ka for the dissolved acid is smaller
than 10-11 or if its starting concentration is less than 10-6 M, then the
initial 10-7 M contribution of protons from water must be included in
the “I” line of the ICE table).
¾ To answer this question we must set up and solve an ICE in much the
same manner as we did in the preceding fundamentals of chemical
equilibrium section. The extent of hydrolysis will depend upon the size
of the Ka and the starting concentration for the acid. When Ka is very
small, as is the case here, and the starting concentration of
appreciable size (greater than 0.001 M), the reaction will proceed to
only a tiny extent, and thus the 5 % will apply, thereby simplifying the
algebraic solution.
ICE Table:
E(M) 0.010 – x - x x Ca
= 2.8 × 10 > 1000
5
Invoke 5% rule Ka
∴ Small K problem
E(M) (≈ 0.010 ) x x
The error is clearly far less than the 5% max. allowed and thus our
approximation was valid.
[H3O + ]equil
Percent Dissociation = × 100%
[HA]initial
For a weak base, the corresponding equation would be
[OH - ]equil
Percent Dissociation = - × 100%
[A ]initial
This plot shows that the extent is reaction is determined not only by the size
of the K value, but also upon the starting concentration for the acid or base.
¾ Bear in mind that although dilution does indeed increase the extent of
hydrolysis, the net effect is, nonetheless, a decrease in either the
proton concentration (for an acid hydrolysis equilibrium) or the
hydroxide ion concentration(for a base hydrolysis equilibrium).
¾ Also, it should be pointed out here that all acids and bases(weak and
strong) at infinite dilution are 100% dissociated and the solution
pH = 7.00.
Answer:
Consider the weak acid hydrolysis equilibrium
then Ka = x 2
; Now we dilute the solution by a factor of 10:
[HA] 2
⎛ x⎞
⎜ ⎟
Qa = ⎝ ⎠
10
⎛ [HA] ⎞
⎜ ⎟
⎝ 10 ⎠
(At this stage, the initial concentrations of all species are decreased by a
factor of 10)
Simplification gives
⎛ x2 ⎞ ⎛ x2 ⎞
⎜ ⎟ ⎜ ⎟
⎝ 100 ⎠ 100[HA] 2
= ⎝ ⎠ =
Qa = x
⎛ [HA] ⎞ (10 ) 10 [HA]
⎜ ⎟
⎝ 10 ⎠
1 ⎛ x2 ⎞
So, Qa = ⎜ ⎟ Qa = 1/10 Ka
10 ⎝ [HA] ⎠
Since Q is less than K, the equilibrium will shift to the right to reestablish
equilibrium. (i.e. the system must bump up [H3O+] and [A-] above 1/10
original and push down [HA] below 1/10 original to raise Q back up to K).
This shift will cause the percent dissociation to increase. Thus, dilution is a
Le Chatelier stress upon the system that the system alleviates by shifting the
equilibrium to the side of the equation with ions.
Weak Base Hydrolysis Equilibrium Problems
¾ Weak bases (such as NH3) react with water by abstracting protons
from water molecules, thereby increasing the [OH-] concentration.
( x) × ( x) x2 (Equation1)
Ka = =
( y − x) y−x
Note that [HA] at equilibrium is equal to y-x in the Ka expression and
that not only is x equal to the equilibrium concentrations for
hydronium ion and conjugate base, it also represents the amount of
HA that ionizes.
¾ At this stage we have two unknowns (assuming the Ka is available) but
only one equation. To find both x and y and solve the equation, we
need to develop a second equation involving x and y. Luckily, there is
another acid-base equation involving both x and y that we can use for
our purposes.
¾ When our particular variables, as defined above, are inserted into this
expression we end up with a second equation containing x and y, viz.
Percent Ionization
e.g. We can replace x in Equation 1 with ×y
100%
which will produce an equation that has only the variable y. Once we
have found y using algebra, x is readily found via substitution back
into either Equation 1 or Equation 2.
¾ This shift will, of course, also drive down the [H3O+]. Thus, adding the
common F- ion to the solution causes a shift towards the
undissociated acid. The net result of the addition of a common ion,
therefore, is a repression of the hydrolysis reaction, in this case acid
hydrolysis.
Common Ion Effect Practice Problem:
[HA]
- is the buffer ratio
[A ]
e.g. For an acidic buffer solution (one with a pH < 7):
HA(aq) + H2O(l)
H3O+(aq) + A−(aq)
(acid) (conjugate base)
I(M) Ca - ≈0 Cb
C(M) – x - +x +x
E(M) Ca – x - x Cb + x
≈ Ca ≈ Cb
[H 3O + ][A - ]
( Ca and Cb >> [H3O+ ], [ OH−] ); Ka =
[HA]
[HA] [HA]
[H 3O ] = K a
+
- ; - is the buffer ratio
[A ] [A ]
⎛ [HA] ⎞ ⎛ [A - ] ⎞
pH = pK a + - log ⎜ - ⎟ or pH = pK a + log ⎜ ⎟
⎝ [A ] ⎠ ⎝ [HA ] ⎠
B(aq) + H2O(l)
BH+(aq) + OH−(aq)
(base) (conjugate acid)
⎛ [B] ⎞ ⎛ [BH + ] ⎞
pOH = pKb + - log ⎜⎜ + ⎟⎟ or pOH = pKb + log ⎜ [B] ⎟
⎝ [BH ] ⎠ ⎝ ⎠
Buffering Action
¾ When a strong acid is added to an HA/A− buffer solution, the added H+ ions
react essentially to completion with the conjugate base A− (via OH− and the
self-ionization reaction for water) because the Kneutralization for this process is
large:
H3O+(aq) + A−(aq)
HA(aq) + H2O(l) Kneut >103
(products strongly favoured)
HA + H2O
A− + H3O+
If [HA] and [A-] are large compared to the amount of H3O+ or OH− that
is added, then the concentrations of [HA] and [A−] will change by only
by small amounts and thus buffer ratio will also change very little, and
thus the pH will increase or decrease only very slightly.
The buffering agents in the water, viz. HA and A−, react with the
added hydroxide ions or protons, respectively, and thereby severely
curtail the change in pH. Essentially, the A− in the buffer converts the
added strong acid H3O+ in to the much weaker acid HA, while the HA
present converts the added strong base OH− into the much weaker
base A− and, in both instances, the solution experiences, as a result,
only a minor alteration in the pH.
Most Effective Buffers
Thus, pH = pKa
¾Ideal buffers are effective up to a pH change
of ± 1 unit. Once the buffer ratio drops below
0.1 or climbs above 10, the solution can no
longer buffer to any appreciable extent. In other
words, the buffer capacity is almost completely
exhausted once the pH has been changed by 1
unit.
Titration Curve for the Titration of a Strong Acid with a Strong Base
¾ This quality combined with the fact that the initial pH for a
strong acid is small causes the strong acid titration curve
to have a large pH change near the equivalence point.
1 K
K overall = K a × = a
Kw Kw
1
(Note : = 1.00 × 1014 M −2 )
Kw
−5
CH3COOH(aq) + H2O(l)
CH3COO (aq) + H3O (aq) Ka = 1.76 × 10 M
- +
+
1
H3O+(aq) + OH-(aq) 2H 2 O(l) = 1.00 × 1014 M −2
Kw
________________________________________________________
Net Rxn:
CH3COOH(aq) + OH-(aq) H2O(l) + CH3COO-(aq) Ka
K overall =
Kw
1.76 × 10−5 M −1
K overall = = 1.76 × 10 9
M (v.large)
1.00 × 10 M
−14 2
We can conclude, therefore, that the reaction will proceed 100 % to the right
and the neutralization will be essentially quantitative.
¾ A generic weak acid-strong base titration curve is shown
below.
¾ Weak Acid-Strong Base Titration Curves Have
Six Distinct Points/Regions, as indicated in the
previous figure:
¾ In this region, some OH- has been added, but not sufficient to
neutralize all of the acid present. More specifically, the ratio in this
region falls between 10 and 1/10.
CH3COOH(aq) + OH-(aq)
CH3COO-(aq) + H2O(l)
⎛ [A- ] ⎞
pH = pK a + log ⎜ ⎟
⎝ [HA] ⎠
4. Mid-Point of the Titration (Middle of the Buffer
Region)
A-(aq) + H2O(l)
HA(aq) + OH-(aq)
¾ In this section of the course we will consider equilibria arising from sparingly
soluble solids dissolving to form aqueous solutions of ions.
Ca3(PO4)2(s)
3Ca2+(aq) + 2PO43-(aq)
If a common ion is present, however, the solubility will vary with the
concentration of the common ion (i.e. the common ion represses
dissolution).
Relative Solubilities
1) CuS(s)
Cu2+(aq) + S2-(aq);
x moles/L CuS ⎯⎯ → x moles/L Cu2+(aq) + x moles/L S2-(aq)
(molar solubility)
1 part CuS gives 1 part Cu2+ and 1 part S2-
x moles/L Ag2S ⎯⎯
→ 2x moles/L Ag+(aq) + x moles/L S2-(aq)
(molar solubility)
Solution:
First we have to determine the equilibrium solubility for
PbI2 in moles per liter (i.e. the amount that must dissolve
to form a saturated solution).
⎛ 0.060 g PbI 2 ⎞ ⎛ 1mol PbI 2 ⎞ ⎛ 1000 mL ⎞ −3
⎜ ⎟ × ⎜ ⎟ ×
s (molar solubility) = ⎝ 100. mL ⎠ ⎝ 461 g PbI 2 ⎠ ⎝ 1 L ⎠⎜ ⎟ = 1.3 × 10 moles/L
PbI2(s)
Pb2+(aq) + 2I-(aq)
¾ Now let’s see what happens when the water contains one of the ions
present in the dissolving salt.
AgCH3COO(s)
Ag+(aq) + CH3COO-(aq)
If we add Ag+ (as AgNO3), the equilibrium will shift to the left, forming more
solid :
AgCH3COO(s) ← Ag+(aq) ↑ (Conc’n Increases) + CH3COO-(aq)
The net result is that the solid has a lower solubility if external Ag+ ions (or
acetate ions) are added to the solution.
Sample Problem:
Calculate the solubility of PbI2 at 25oC in a 0.0100 M
solution of NaI(aq).
Precipitation Reactions
¾ A complex ion is a stable ion composed of many atoms that has been
formed by coordination (attachment) of anions or neutral molecules to
a central metal atom or ion.
¾ The anions or neutral molecules bound to the metal centre are called
ligands.
¾ Each ligand donates at least one pair of electrons to the central metal
atom.
e.g.
NiSO4(s) + 6H2O(l)
[Ni(H2O)6]2+(aq) + SO42-(aq)
(Ammonia adduct of BF3 (Molecule (C)): the BF3 has been stuck on the
lone pair of the NH3 molecule)
The B-N bond H3N−BF3 in the adduct is called a coordinate covalent or
dative covalent bond.
¾ Similarly, the formation of a transition-metal complex can
be viewed as a Lewis acid-Lewis base reaction.
Microscopic view
Complex-Ion Equilibria: Formation Constants for
Complex Ions
Step 1
[Ag(NH 3 )]+ −1
[Ag(NH3)]+(aq) K1 = = × 3
Ag+(aq) + NH3(aq) [Ag + ][NH 3 ]
7.1 10 M
Step 2
[Ag(NH3)]+(aq) + NH3(aq)
[Ag(NH3)2]+(aq) [Ag(NH 3 ) 2 ]+
K2 = = 2.3 × 103 M −1
[Ag(NH 3 )]+ [NH 3 ]
Ag+(aq) + 2NH3(aq)
[Ag(NH3)2]+(aq)
[Ag(NH 3 ) 2 ]
+
7 −2
Kf = + 2
= 1.6 × 10 M
[Ag] [NH 3 ]
¾ The large value for the Kf indicates that the complex ion product is
strongly favoured.
¾ Most formation constants for complex ions are quite large. This suggests
that these species are very stable compared to the free ligand and
uncomplexed metal ion.
Practice Problem: Complex Ion Formation
+ +
[Ag(NH ) ] 7
Ag (aq) + 2NH3(aq)
+
[Ag(NH3)2] (aq) f
+ K = =
3 2
1.6 × 10 M
−2
+ 2
[Ag] [NH ] 3
_________________________________________________________
AgCl(s) + 2NH3(aq)
[Ag(NH ) ]+(aq) + Cl-(aq)
3 2
Ko = Ksp x Kf = 2.9 x 10-3 M-1
CuS(s) + 4NH3(aq)
[Cu(NH3)4]2+(aq) + S2-(aq)
Thermodynamics
Internal Energy(U): Sum of all of the kinetic and potential energies for
all of the particles of the chemical or physical system
What is Chemical Energy?
Consider the reaction
CH4(g) + 2O2(g)
CO2(g) + 2H2O(g) + “Energy”
¾ State properties depend only on the state of the system and not how it
was reached.
e.g. State Properties: A man is standing upright on the summit of
Mount Everest. How he arrived at the summit is a path function :
a) Perhaps he parachuted on to the summit from a Boeing 747 jet.
b) Maybe he was carried up to the top of Everest by some Sherpas.
c) It could be that he was beamed to the pinnacle using the transporter
system of the Starship Enterprise.
a, b and c are possible pathways which might have been used to end
up in the “state” of standing erect on Everest.
e.g. 1.0 mol of a gas at 300 K and 2.0 atm is in a definite,
fixed energy state.
q and w are not state functions, but rather pathways by which the
state achieves a certain internal energy.
Sign Conventions for the Internal Energy Change Equation
¾ Many chemical reactions occur in the open air and thus are subjected to
a constant pressure (i.e. atmospheric pressure)
e.g.
2C8H18(l) + 25O2(g)
16CO2(g) + 18H2O(g) + “Heat” (Fire Bomb)
¾ In this case the energy exchange between the system and the
surroundings is not restricted just to heat flow (qp).
ΔH = ΔU + PΔV
(Enthalpy Change Equation)
P∆V = ∆ngRT
(at constant P and constant T, according to the ideal gas law)
ΔH = ΔU + Δn g RT
∆H = ∆U when
¾ The device used to determine the heat changes (read energy changes)
associated with chemical reactions is called a calorimeter (from the
old energy unit the calorie, which is the energy needed to raise one
gram of water by one degree centrigrade).
¾ Calorimeters measure heat flow by recording the temperature change
that occurs when the calorimeter and its contents absorbs or discharges
energy as heat.
J J
Units : or o
K•g C•g
J J
Units : or o
K • mol C • mol
e.g. H2O has a relatively high specific heat capacity of
4.184 J
K•g
while metals have much smaller specific heat capacities.
e.g. Fe(s) = 0.45 J
K•g
(Note 1.000 calorie = 4.184 J)
Measuring the Heat of Solution
(the solution in the cup, excluding the reacting molecules and the cup
itself, constitute the surroundings).
Thus,
⎛J⎞ ⎛ J ⎞
Ccalorimeter = Heat capacity for the empty calorimeter ⎜ ⎟ or ⎜ o ⎟
⎝K⎠ ⎝ C⎠
¾ The enthalpy change for a chemical reaction (∆H) is not dependant upon the
pathway (enthalpy change is a state function).
¾ Thus, the enthalpy change for a given reaction is the same, regardless of
whether the transformation occurs in one step or several steps.
In order to use Hess’s law properly, we must keep in mind the following rules:
H2(g) + 1/2O2(g)
H2O(l) ∆Hof H2O(l)= -285.8 kJ/mol
Remember that
ΔH o rxn = ∑ ΔH o
f (products) − ∑ ΔH o f (reactants)
Covalent Bond Energies: Use of Bond Energies to
Estimate ∆H Values
¾ For reactions in the gas phase, the heat of reaction can be estimated
by considering which bonds are broken and which are formed during
the course of the reaction. In other words, the use of covalent bond
energies is yet another way in which ∆H can be calculated.
e.g. Cl2(g) + hv
2Cl (g)
¾ Bond energies are positive since energy is needed to
break covalent bonds.
2H(g)
H2(g) + energy
H2(g)
2H(g) ∆Ho = + 436 kJ/mol rxn
¾ For all diatomic molecules, the bond energy is the energy
required to split the gaseous molecule into its atoms:
X2(g)
2X(g)
¾ At the start, each O-H bond has the same strength, but
once the first bond is broken, the second becomes easier
to break (energized OH is activated for bond scission):
H2O(g)
H(g) + OH (g) ∆Ho = + 498 kJ/mol rxn
OH(g)
H(g) + O(g) ∆Ho = + 428 kJ/mol rxn
kJ kJ
498 + 428
Thus, Av. OH bond energy for H2O = mol mol kJ
= 463
2 mol
Notes on Bond Energies
S(s)
S(g) ∆Ho = + 278.8 kJ
F2(g)
2F(g) ∆Ho = + 158 kJ
S(s) + 3F2(g)
SF6(g) ∆Ho = -1209 kJ
Solution:
S-F(g)
S(g) + F(g)
Note: All species must end up in the gas phase for this
procedure to be valid.
This is simply another application of Hess’s Law:
1. S(s)
S(g) ∆Ho1 = + 278.8 kJ/mol
+
2. 3 x (F2(g)
2F(g) ) ∆Ho2 = 3 x 158 kJ/mol
+
3. S(g) + 6F(g)
SF6(g) ∆Ho3 = negative
_____________________________________________
4. S(s) + 3F2(g) SF6(g) ∆Ho4 = -1209 kJ/mol
¾ The ∆H for a chemical reaction can also be calculated via the bond
energies for the constituent bonds in the reactants and products. This
procedure only works with all species in the gas phase and when all
reactant molecules are broken apart into their constituent atoms. Product
molecules are then assembled from the appropriate free atoms in the gas
phase (vide infra):
Atoms
Bond Scission Bond Formation
Reactant Product
Molecules ∆Ho rxn Molecules
ΔH o rxn = ∑ Bond Energies for Bonds Broken in the Reactants −
H2O(l)
H2O(g) ∆H = + 41 kJ/mol
¾ Thus, the evolution of heat cannot be the only driving
force. There must be another factor that determines
whether or not a process is spontaneous.
¾ More specifically,
ΔH fus
ΔSfus =
Tm.p.
(ΔH is the molar enthalpy of fusion; Tm.p. is the melting point (K))
and
ΔH vap
ΔSvap =
Tb.p.
(ΔH is the molar enthalpy of vapourization; Tb.p. is the boiling point (K))
¾In both cases, energy must be added to bring about the phase change
and this energy comes from the surroundings.
Since these are equilibrium processes,
Consequently,
¾ Also, the more ordered the substance is, the less effectively it
dilutes energy, and hence the smaller is its standard molar
entropy.
e.g. Consider the three allotropes of carbon, viz.
J J
Graphite So = 5.74 ; Diamond So = 2.42
K• mol K• mol
J
Buckyball (C60) So = 7.30
K• mol
Of the three, diamond is the poorest at diluting energy owing to its rigid,
highly-ordered internal structure;
ΔSo rxn = ∑ So
(products) − ∑ (reactants)
So
a) F2(g)
2F(g)
b) CO(g) + Cl2(g)
COCl2(g)
The Second Law of Thermodynamics
¾ This does not mean that the change in the entropy for the system or
its surroundings cannot be negative. To be spontaneous, these two
terms simply must sum to a value greater than zero.
¾ For reversible processes, the total entropy change for a system and
its surroundings is zero.
¾ So, heat flow into the surroundings increases the entropy of the
surroundings and vice versa.
ΔG = ΔH − T Δ S
(Gibbs-Helmholtz Equation)
Thus, the reaction will proceed to the right (forward direction) to bump
up the concentration of products at the expense of reactants to make
∑ G o
Products = ∑ Reactants
G o
Thus, the reaction will proceed to the left (reverse direction) to bump
up the concentration of reactants at the expense of products to make
∑ G o
Products = ∑ Reactants
G o
2NO2(g)
N O (g)
2 4
2NaF(s)
2Na(s) + F2(g)
C5H12(l) + 8O2(g)
5CO2(g) + 6H2O(g)
Estimating the Temperature at Which an Enthalpy/ Entropy-
Driven Reactions Becomes Thermodynamically Possible
¾ If ∆Ho and ∆So for the reaction are known, we can estimate the transition
temperature, at which the reaction reverses spontaneity.
ΔH o
Ttrans =
ΔSo
VERY IMPORTANT: ∆Go = ∆G = 0 ONLY AT Ttrans for entropy or
enthalpy-driven reactions.
At Ttrans , K =1 and reactants/products are preferred equally
Estimating ∆Go at Temperatures Other than 25oC
CH4(g) + H2O(g)
3H2(g) + CO(g)
ΔG o rxn = ∑ f
ΔG o
(products) − ∑ f (reactants)
ΔG o
and
ΔG o f = ΔH o f − T Δ So f
Definition: ∆Gof is the change in standard free energy
that accompanies the formation of one mole of a
substance in its standard state from its elements in their
standard states (usually at 25oC). Tabulated values on the
data sheet are for 25oC.
The driving force and the direction of the reaction depend upon the
concentrations of reactants/products (i.e. upon Q) and also on the
magnitude/sign of the ∆Gnon-std for the reaction.
¾ As the reaction proceeds, the instantaneous value of
∆Gnon-std varies as Q changes.
ΔG non-std = ΔG o + RTlnQ
J
R = 8.3145 K• mol ; K is the temperature in Kelvins
2NOCl(g)
2NO(g) + Cl2(g)
Replacing the ∆Go term in ∆Go = -RTlnK with ∆Ho - T∆So and solving
for K gives
ΔH o ΔSo
ln K = − +
RT R
(Van’t Hoff Equation)
⎛ K 2 ⎞ ΔH o ( T2 − T1 )
ln ⎜ ⎟= × Where T2, T1 are temperatures in Kelvin; K2 and K1 are
N2O4(g)
2NO2(g)
¾ The two types of processes that we will study in this course are:
Cr2O72-(aq) + C2O42-(aq)
Cr2+(aq) + CO2(g)
II) Reactions in Basic Solution
Same basic approach as with balancing in aqueous
solution, but with two additional steps:
MnO4-(aq) + N2H4(aq)
MnO2(s) + N2(g)
Galvanic Cells
¾ The circuit for the cell is closed via a conducting wire and a salt
bridge or semi-permeable membrane.
¾ One of the earliest galvanic cells assembled was the Zn-Cu battery.
This particular cell is based upon the following redox reaction:
¾ Remember: “Anions flow into the anode, while cations flow into the
cathode”.
¾ These ions can pass between the two half cells either through a salt
bridge or a porous membrane.
¾ Galvanic cells are usually reported in standard cell notation (vide infra):
¾ The difference in the electrical potential between the cathode and the
anode of a voltaic cell creates an electromotive force that drives
electrons through the external circuit.
¾ The maximum electrical work that can be done during the transfer of Q
coulombs of charge by an electromotive force of E volts is given by
¾ Therefore,
Maximum work = ∆G = − Q × E
ΔG = − n × F × E
(E = max . possible potential for the cell at std. conditions )
Spontaneous Redox Reactions
Stronger Oxidizing Agent + Stronger Reducing Agent Weaker Reducing Agent + Weaker Oxidizing Agent
Note: The cell reaction with the highest positive potential is the one that will
occur preferentially, unless it is kinetically-controlled.
¾ When two half reactions are obtained to give a third half-reaction, all of
the same type, the potential for the third half-reaction is not the sum of
the potentials for the first two, but rather the weighted average of the first
two potentials. This is the case because the half-reactions are all of the
same type (no electrons are cancelled out) voltages are blended
proportionately rather than simply added together.
i.e. ΔG o 3 = ΔG o1 + ΔG o 2
e.g. Determine the reduction potential for
Cu2+(aq) + 2e- Cu(s) given…
Solution:
Eoc =
( −1 × 0.153 V + − 1 × 0.521 V )
= 0.337 V (weighted average)
−2
Practice Sample Problem: Calculating Half –Cell Potentials/Latimer
Diagrams
- 0 . 94 V 0 . 98 V
NO3 HNO2 NO
(V) (III) (II)
a) Write the equation for the NO3-/NO couple in acidic solution and
calculate its reduction potential.
b) Write a balanced equation for the disproportionation of HNO2. Is the
disproportionation of HNO2 spontaneous at std. conditions/25oC?
Cell Potential and Concentration: The Nernst Equation
2. An increase in [H+] or [Cl-] will drive the reaction back to the left,
thereby making the cell voltage less positive.
The reduction potential becomes more positive with increasing [Ox] and
decreasing [Red].
RT
E = E − o
ln Q where
nF
¾ This powerful equation gives the voltage for non-standard cells and
half-cells (i.e. cells in which at least one concentration or pressure is
different from 1M or 1 atm).
¾ By combining all of the constants, fixing the temperature
at T = 298 K and converting ln into log base 10 we get the
more commonly used version of the Nernst equation,
shown below:
0.0592
E = E − o
logQ (for 298 K only!)
n
Solution:
¾ Electrons flow from the anode into the cathode; this will cause an
increase in [Ag+] in the anode and a decrease [Ag+] in the cathode.
⎡⎣ Ag + (aq )(anode) ⎤⎦
n = 1e- ; Q =
⎡⎣ Ag + (aq )(cathode) ⎤⎦
0.0592 ⎛ [0.10 M ] ⎞
E = 0.000V − log ⎜ ⎟V
1 ⎝ [1.0 M ] ⎠
E = 0.0592 V
Sample Problem: Concentration Cells
Given that the initial voltage of the cell below is 1.41 V at
25oC, calculate the Ksp for Tl3PO4.
Tl(s)/Tl+(aq) ( x M)//Tl+(aq) (1.00 M)/Tl(s) (Assume that the
anodic solution is saturated Tl3PO4(aq) produced by
dissolving solid Tl3PO4 in pure water)
Calculating Keq Values from Standard Potentials
n
log K = Eo
0.0592
(relates std. cell voltage to equilibrium constant at 25oC)
Practice Problem: Std. Voltage and the Equilibrium
Constant
¾ The voltage for this cell at the instant of hook-up is – 1.10 V. (The
voltage for an electrolytic cell is always negative)
¾ The Zn/Zn2+ electrode is the cathode, the Cu/Cu2+ electrode the anode
¾ The negative terminal of the power source sends electrons
to the cathode while electrons from the anode are pulled to
the positive terminal of the power source.
Voltaic + -
Electrolytic - +
¾ Also, keep in mind that in both voltaic and electrolytic cells,
reduction occurs at the cathode and oxidation occurs at the anode.
¾ Additional voltage over and above the EMF for the voltaic cell is required
to initiate electrolysis.
¾ The major reason for the need to use higher voltage is kinetic
overpotential, which is the extra voltage needed to overcome the
activation energy for each half-reaction and drive the electrons across
the electrode surface at a reasonable rate.
One question that arises is: “In what order would the metals plate out
into the cathode?”
¾ The reaction with the more positive Eo has the greatest tendency to
proceed.
¾ This is the correct order but only because of the high
overpotential associated with the reduction of H2O(l).
Reduction of H2O(l)
Oxidation of H2O(l)
¾ However, due to the high overvoltage for the reduction of liquid water,
the actual reduction of pure liquid H2O is - 0.814 V.
¾ Thus, one can actually reduce metal ions with Eored as low as – 0.80 V
in liquid water.