Chemical kinetics

(Nazaroff & Alvarez-Cohen, Section 3.A.2)

This is the answer to what happens when chemical equilibrium is not reached.
For example, take the two-way reaction

A + B C + D
As A and B come into contact with each other, they start to react one with the other,
and the reaction rate can be expressed as

Rforward = kf [A] [B].

This expression reflects the fact that the more A and B there is, the more encounters
occur, and the more reactions take place.
This rate depletes the amounts of both A and B, and generates amounts of C and D:

d [A] d [B]

Rforward k f [A][B]
dt
dt
d [C] d [D]

Rforward kf [A][B]
dt
dt

But, at the same time, C and D come in contact, too, and carry their own (reverse) reaction,
at a rate proportional to their amounts

Rreverse = kr [C] [D] .

This rate depletes the amounts of both C and D, and adds to the amounts of A and B:

d [A] d [B]

Rreverse k r [C][D]
dt
dt
d [C] d [D]

Rreverse k r [C][D]
dt
dt
Because the two reactions occur simultaneously, we subtract the rate of one from the other:

d [A] d [B]

Rforward Rreverse kf [A][B] k r [C][D]

dt
dt
d [C] d [D]

Rforward Rreverse kf [A][B] k r [C][D]

dt
dt

Finally, in a system with open boundaries, we can add the imports and exports:

d [A]
Qin [A]in Qout [A]out k rV [C][D] k f V [A][B]
dt
inlets
outlets
d [B]
Qin [B]in Qout [B]out k rV [C][D] kf V [A][B]
V
dt
inlets
outlets
d [C]
Qin [C]in Qout [C]out k f V [A][B] k rV [C][D]
V
dt
inlets
outlets
d [D]
Qin [D]in Qout [D]out kf V [A][B] k rV [C][D]
V
dt
inlets
outlets
V

imports

exports

sources

sinks

where V is the volume of the system for which the budget is written.
Note: The variables here are concentrations ([]s), expressed in moles per liter
(mol/L or M), not in mass per liter (such as mg/L). The latter would be obtained
after invoking the molecular weights of the individual chemicals.

Chemical Kinetics Reaction order

(Nazaroff & Alvarez-Cohen, Section 3.A.3)
The previous example assumed that it takes two chemicals for each reaction.
This is not always the case. For example, when a substance dissolves in water

H2CO3 H+ + HCO3
The forward reaction needs only one concentration

Rforward = kf [H2CO3]

Nomenclature:
Second-order reaction:

First-order reaction:

Zeroth-order reaction:

d [A]
k [A][B]
dt
d [A]
k [A]
dt
d [A]
k
dt
Note: The units of the k coefficients vary accordingly!

Equilibrium & Kinetics of Phase Change

(Nazaroff & Alvarez-Cohen, Exhibit 3.A.1 pages 90-92)

Consider a closed vessel half filled with water

and topped with air. As we can expect, some of
the water evaporates into the air, and some of the
water vapor in the air will condense back into
liquid water. The two processes of evaporation
and condensation will eventually come to
equilibrium and set a certain level of moisture in
the air above the water.

Evaporation :

Revap ke S

where

S surface of contact

Condensation :

Rconden kc SC

where

C concentration of water in the air (moisture)

Vair

dC
Revap Rconden
dt
ke S kc SC

dC ke kc
C
dt H H

where

Vair
S

is the height of the air layer

dC ke kc
C
dt H H
If C (t 0) 0 (initially dry air), then the evolution of the water vapor in the air
over time is

C (t )

ke
kc

kc
1 exp H

Eventually, equilibrium is reached

for which

ke
kc

Concentration of water vapor in the air can be transformed into partial pressure
of water vapor.
Water weighs 18 grams per mole. Thus, the number of moles of water vapor
per volume of air is

nwater C grams/volume

Vair
18 grams/mole
and the partial pressure of water vapor is (assuming that it behaves as an ideal gas):

Pwater

nwater
C
RT RT
Vair
18

Chemical Equilibrium
(back to beginning of Nazaroff & Alvarez-Cohen, Section 3.A.2)

A system is in chemical equilibrium when

1. It does not vary in time (steady state);
2. It is well mixed;
3. There is no net flow of mass, heat or species with the surroundings;
4. The net rate of all chemical reactions is zero.
Such a state corresponds to a local minimum in free energy:

G G 0 RT ln(Q )
0

where Q

[C ]c [ D]d
[ A]a [ B ]b

For the reaction

G = 0 implies Q = constant.

sum of free energies of

components under
standard conditions

is called the reaction quotient.

a A+ b B c C+d D
There is a better to see this, though

Many chemical reactions in the environment are two-way reactions.

Symbolically,

A + B C +D
during which A and B react to produce C and D, and at the same time
C and D react to produce A and B.
The rate of reaction between A and B is
The rate of reaction in the reverse direction is

Rforward = kf [A] [B]

Rreverse = kr [C] [D]

Chemical equilibrium occurs when the two rates equal each other so that
the rate of depletion of A and B equals the rate of their replenishment:

kf [A] [B] = kr [C] [D]

That is, when:

[C ] [ D ] kf
const.
[ A] [ B ] k r

Equilibrium constant
from equilibrium the equilibrium equation kf [A] [B] = kr [C] [D]
we can write

[C][D] kf
K
[A][B] k r

The constant K is determined in the laboratory.

It typically varies with temperature.

Generalization to reaction with arbitrary numbers in the stoichiometry:

aA + bB cC + dD
Rforward = kf [A]a [B]b
Equilibrium exists when

Rreverse = kr [C]c [D]d

kf [A]a [B]b = kr [C]c [D]d

[C]c [D]d kf
K
[A]a [B]b k r

Important particular case: Water dissociation

(Nazaroff & Alvarez-Cohen, Section 3.C.2)

Water always tends to dissociate a little, via the reaction

H2O H+ + OH

There is an equilibrium constant for this, and it is:

[H ] [OH ]
1.83 10 16 moles/L
[ H 2 O]
Since [H2O] is always the same and equal to 55.4 moles/L (see Lecture 2),
we can write:

[H ] [OH ] (1.83 10 16 mol/L) [H 2 O]

(1.83 10 16 mol/L) (55.4 mol/L) 1.01 10-14 (mol/L)2

pH of Pure Water
In the absence of any other ion (pure water!),
to any [H+] ion there is a companion [OH] ion. Thus,

[H ] [OH ]

It follows

[H ] 1.01 10 14 ( mol/L) 2 1.0 10 7 mol/L

pH log10 [H ] 7.0

Inorganic impurities in water and air

First, a distinction needs to be made between organic and inorganic compounds:
organic compounds = those with carbon,
except for elemental C, CO, CO2, HCO3 and CO32
Acids & Bases:
acids make H+
common acids are HCl, HOCl, H2S, H2SO4, H2SO3, HNO3
bases make OH
common bases are NH3, NaOH, CaCO3, Ca(OH)2
OH takes away H+ via

OH + H+ H2O

Dissolution in water ions

cations are positive, anions are negative
most common ions are NH4+, Na+, Ca2+, Cl, SO42, HCO3, CO32

Electroneutrality Principle
(Nazaroff & Alvarez-Cohen, page 45)

It can almost always be assumed that the initial water solution is electrically neutral,
that is, it has no net electric charge. Then, conservation of electrons demands that this state
of neutrality persist over time.
Therefore, for every extra electron on an anion in the solution, there must be a missing
electron from a cation in the same solution, and

zi [Ai] = 0
where

zi = charge of ion Ai (+ for cation, for anion), most often +1, +2, 1 or 2
[Ai] = molar concentration of ion Ai .

Example: The Carbonate System

(Nazaroff & Alvarez-Cohen, section 3.C.4)
Carbon dioxide CO2 from the atmosphere partially dissolves in water.
In water, it then forms carbonic acid H2CO3.
In turn, H2CO3 dissolves into H+ and bicarbonate ion HCO3,
and HCO3 into another H+ and carbonate ion CO32.
Thus, the following reactions take place in water exposed to the atmosphere:

CO2 + H2O H2CO3

H2CO3 H+ + HCO3
HCO3 H+ + CO32
In addition, water H2O always decomposes slightly into H+ and OH:

H2O H+ + OH
Electroneutrality requires:

[H+] = [HCO3] + 2[CO32] + [OH]

The equilibrium relations are:

CO 2 in the water CO 2 in the air

[CO 2 ] K H PCO 2 , K H 0.034 M/atm

CO 2 in the water H 2O H 2 CO 3

[H 2 CO 3 ]
1.58 10 3
[CO 2 ]

H 2 CO 3 H HCO 3

[H ] [HCO3 ]
2.834 10 4 M
[H 2 CO 3 ]

HCO 3 H CO 32

[H ] [CO 32 ]
4.68 10 11 M
[HCO3 ]

H 2 O H OH

[H ] [OH ] 10 14 M 2

Do we have enough equations?

Number of unknowns = 6 for [CO2] , [H2CO3] , [HCO3] , [CO32] , [H+] and [OH]
Number of equations = 6 = 5 (above) + 1 (electroneutrality at bottom of previous slide).
So, yes, we have enough equations to solve the problem.

399
For a partial pressure of CO2 in the atmosphere equal to 350 ppm, we have
399

1.36

[CO 2 ] (0.034 M/atm) (350 10 6 atm) 1.19 10 5 M

From the first chemical equilibrium, we deduce:
1.36

2.14

[H 2 CO 3 ] (1.58 10 3 )[CO 2 ] (1.58 10 3 )(1.19 10 5 M ) 1.88 10 8 M

We solve the remaining simultaneous equations and obtain:

[HCO 3 ] 2.31 10 6 M
2
3

[CO ] 4.67 10

11

2.46 x 10-6 M
4.67 x 10-11 M

[OH ] 4.33 10 M

4.06 x 10-9 M

[H ] 2.31 10 6 M

2.47 x 10-6 M
5.608

Thus, the pH of natural (clean) water is

pH log10 [H ] 5.64

Clean, natural water is slightly acidic.

And, it is getting increasingly acidic. There is fear that coral in the sea will not survive.

http://coralreef.noaa.gov/education/oa/resources/22-4_kleypas.pdf

Question: What can be done about coral erosion short of curbing CO2 in the atmosphere?
Answer: Use calcium, or simply rely in the calcium that is naturally there.

CaCO 3 Ca CO 3
CO 3 H HCO 3
HCO 3 H H 2 CO 3
H 2 CO 3 H 2 O CO 2
CO 2 in water CO 2 in air

The net effect of limestone is to deliver calcium ions that displace protons,
and thus reduce acidity.
There is efficiency in this because one Ca++ eliminates two H+s.

But think:
- If a body of water has become too acidic because of some acid input,
it is better to eliminate that acid source than to remediate the water body.
- Often, acidity comes from acid precipitation (rain / snow) over the lake.
- This atmospheric acidity is primarily in the form of sulfuric acid (H2SO4)
and nitric acid (HNO3).
- Sulfuric acid is the consequence of burning coal with sulfur content,
creating SO2 in the combustion fumes that later turn into H2SO4.
- Nitric acid originates from NO2 out of tailpipes of gas and diesel engines.
- Solutions therefore consist in
-

Scrubbing the SO2 from fumes before release through the smokestack.
Burning low-sulfur coal.
Burning some fuel other than coal for electricity.
Getting electricity from windmills or other non-fuel alternatives.
Regulate tailpipe emissions.
Have people drive better cars.
Have people drive less
Reduce food shipment by consuming local foods.

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