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Since motion of reacting molecules is (usually) random, reaction rate depends on factors that influence the 2
conditions.
The more collisions that occur, the greater the chance that some of them will have the correct geometry.
The greater the speed (average KE) of the reactants, the more likely some of the collisions will have
enough energy for a successful collision.
5 factors:
-concentration of reactants
-temperature
-surface area of reactants (heterogeneous reactions)
-nature of reactants
-presence of catalysts or inhibitors
Nature of Reactants
Includes:
-shape & size of molecules
-polarity of molecules
-ionic charges (& their magnitude: +1, +2, etc.)
-phase (solid, liquid, aqueous, gas)
-electron affinity
-bond type (ionic, covalent) & strength
-# bonds to break or form
In general, reactions occurring b/w small ionic species in aqueous solution are very rapid (often instantaneous)
Reactions involving large molecules, molecules w/ many bonds to break (or form), or many molecules tend to be
slower
Heterogeneous reactions (those involving different phases) tend to be slow due to limited surface areas;
however, if finely powdered solids react with gases the rate may be fast.
PH
∆
R
E A
PE
heat
content
P
R
E
∆AH PE
heat
content
Exothermic Endothermic
∆H – enthalpy
EA – activation energy
Activated Complex: formed if the colliding molecules have the EA. A species w/ high potential energy but very
unstable (short-lived). If the energy & geometry conditions are met, the activated complex will quickly break into
the products; if not it will break up into the original reactants.
∆H
P
R
EA
==PE
89.5
-77.2kJ
reaction kJ
co-ordinate (or progress of rxn.)
progress
∆H
EArf
PE of rxn.
KE
progress of rxn
EAf = EAr + ∆H
Reaction Mechanisms
aA
E
∆H
creaction
b
intermediates
activated complex:
-unstable, short-lived, high PE species
consisting of the colliding molecules
-bonds are being broken and/or made;
atoms are being re-arranged
Reaction Kinetics
Determining Rate Law from Experimental Data
Rate Law: relationship b/w rate & concentration of the reactants in a reaction
A+B→C+D
rate law: R = k[A]m[B]n
R is the rate w/ units of (mol/L)/s or M/s or mol L-1 s-1
k is the rate constant (specific to each rxn. at given temp)
[A] & [B] are conc. Of reactants A & B
m & n are exponents determined by experimentation
order of reaction: sum of exponents (m + n)
higher order = more complex reaction
Effect of changing the conc. of each reactant must be measured separately. Thus all reactants except 1 must be
held constant. Rate is then measured at several different conc.’s of the reactant in question. Process is
repeated for each reactant. In most reactions the rate is not constant throughout the whole reaction but the
initial rate is customarily used to determine the rate law.
Experiments 1, 2, 3:
When [NO] doubled (0.0010 to 0.0020) rate increased by factor of 4 (0.0020 to 0.0080). when [NO]
tripled (0.0010 to 0.0030) rate increased by factor of 9. The increase in rate is the square of the
increase in conc. so the rate law w/ respect to the NO reactant is R [NO]2.
Experiments 4, 5, 6:
When [H2] doubled from exp. 4 to 5 the rate also doubled. When [H2] tripled the rate tripled. Thus, rate
law is R [H2].
Combined: R = k[NO]2[H2]
Order of rxn.: 3
Pick 2 trials where one reactant conc. changes & the others are constant
rate2/rate1 = (rate law trial 2)/(rate law trial 1) = (k[S2O32-]x2 [I-]y2) / (k[S2O32-]x1 [I-]y1)
therefore
2.0 = (k[S2O32-]x2 [I-]y2) / (k[S2O32-]x1 [I-]y1)
therefore
2.0 = (2.0x10-4)x/(1.0x10-4)x
2.0 = (2.0x10-4/1.0x10-4)x
2.0 = 2.0x
log2.0 = xlog2.0
x = log2.0/log2.0
x=1
Catalyzed Reactions
(homogeneous)
eg. H2O2 + I- → H2O + IO- (slow) reaction intermediate: IO-
IO- + H2O2 → H2O + O2 + I- (fast) catalyst: I-
2H2O2 → 2H2O + O2
Heterogeneous Catalysts
-Usually solids; reactants will be liquid or gas
-ex: platinum in catalytic converter of car’s exhaust system
iron powder & metal oxides in the Haber process (ammonia production)
nickel for changing vegetable oils into ‘solid’ fats (margarine)
-usually 4 steps:
1. adsorption & activation of the reactants
2. migration of the adsorbed reactants on the surface
3. reaction of the adsorbed substances
4. escape (or desorption) of the products
Example
1 CH3OH + H+ → CH3OH2+ (slow)
2 CH3OH2+ → CH3+ + H2O (fast)
3 CH3+ + CH3COOH → CH3COOHCH3+ (fast)
4 CH3COOHCH3+ → CH3COOHCH3+ + H+ (fast)
CH3OH + H+ → CH3OH2+
CH3OH2+ → CH3+ + H2O
CH3+ + CH3COOH → CH3COOHCH3+
CH3COOHCH3+ → CH3COOHCH3+ + H+
H+
Overall rxn: CH3OH + CH3COOH → CH3COOHCH3+ + H2O
Catalyst: H+
PE diagram:
progress of rxn.
PE
cat.
uncat.
Questions:
3. Given the following data write the rate law and the rate constant
Answers:
1. (0.75 mol C12H22O11/min) (12 mol C/1 mol C12H22O11 ) = 9.00 mol C/min
(9.00 mol C/min) (1 min/60 s) = 0.150 mol C/s
(0.150 mol C/s) (10.0 s) = 1.50 mol C
(1.50 mol C) (12.0 g C/1 mol C) = 18 g C
2. 1-higher temp = faster particles, therefore more likely to collide, therefore faster reaction
2-higher temp = more energetic collisions, therefore more molecules have min. Energy requirement
3.
[H2] (M) [I2] (M) Rate (M/s)
x4 R [H2]
x4 0.100 0.100 3.00 x 10-3
x2 R [I2]
0.400 0.100 12.00 x 10-3 x2
R = k[H2][I2]
K = R/[H2][I2]
= (3.00x10-3 M/s)/(0.100 M)(0.100 M)
= 0.3 M-1 s-1
Unit 2: Chemical Eqilibrium
Most reactions don’t go to completion. As product molecules form, they may collide and reform the original
reactants.
A+B↔C+D rate(f) = k[A]x[B]y
rate (r) = k[C]m[D]n
Unless otherwise specified the term ‘reactant’ is still used to refer to things to the left of the equilibrium arrows &
‘product’ refers to those to the right of the arrows.
Initially the forward & reverse rxn’s may have different rates.
Equilibrium: point of time where the f.rate = r.rate; no further changes are visible
Le Châtlier’s Principle
Le Chatlier’s Principle: If a closed sytem at equilibrium is subjected to a change, processes will occur that tend
to counteract that change, and restore equilibrium.
1. Temperature Changes
endothermic: (ex. N2O4 + 59.4 kJ ↔ 2NO2) increased temp means more heat available to the system;
therefore allowing more of the reactant (N2O4) to react. Thus, the system shifts right (more product
produced while the amount of reactant decreases). If the higher temp. is maintained, the system will
establish a new equilibrium, one in which there are more products & less reactants (therefore the Keq is
higher). The opposite occurs in an exothermic reaction
*only factor that will cause the value of Keq to change
new
N
[NO
from
time
x2 x2O
] 24 eq.
at
mole
which
ratio
temp. increases
2. Concentration Changes
If the conc. of a reactant or product increases, the equilibrium will shift to the opposite side.
time
extra
[[NO
N]2O
NO 2
] NO
doesn’t
2
return to
24
injected value
original
3. Volume Changes
-for (g) rxn.’s if vol. ↓ rapidly, the conc. of all gases will ↑ (b/c same # moles in fewer L); an ↑ in conc.
also means ↑ in pressure. To counteract this, system shifts to reduce the total # of moles of gas
-if pressure ↑ due to addition of an inert gas there is no change
-if pressure changes due to change in temp. or # moles the problem is considered to involve only a
N2O
NO
[time
] 24 at which vol.
suddenly decreases
change in temp. or conc. the effects of pressure change are considered insignificant
4. Addition of a Catalyst
-no change if added to equilibrium
addition
N
[NO
time
O
]
2 24
of
catalyst
rate = k[A]a[B]b
at equilibrium f.rate=r.rate
kf[A]a[B]b = kr[C]c[D]d
kf/kr = [A]a[B]b/[C]c[D]d
Keq = [A]a[B]b/[C]c[D]d
Equilibrium expression for a rxn. includes only substances which could undergo a measurable change in conc.
-all gases must be included
-all aqueous ions must be included
-solids not included (density of solid constant under norm. conditions; density=measure of conc. of solid)
-pure liquids not included (same reason as solid). Note that mixtures of miscible liquids must be
included; immiscible liquids are not included.
Ktrial < Keq → system shifts right (more products, less reactants)
Ktrial > Keq → system shifts left (less products, more reactants)
Equilibrium Calculations
Example 1 – A 2.0 L bulb contains 6.00 mol NO2 (g), 3.0 mol NO (g), & 0.20 mol O2 (g) at equilibrium. Calculate
the Keq. 2NO (g) + O2 (g) ↔ 2NO2 (g)
Example 2 – 4.00 mol NO2 (g) is introduced into a 2.00 L bulb. After some time equilibrium is attained according
to the equation 2NO (g) + O2 (g) ↔ 2NO2 (g). At equilibrium 0.500 mol NO (g) is found. What is Keq?
2 .if not at equilibrium, use an I.C.E. table (all values are concentrations)
[NO2]start = 4.00 mol/2.0 L = 2.00 M NO2
[NO]eq = 0.500 mol/2.0 L = 0.250 M NO
2NO (g) +
I 0 0 2.00 O2 (g) ↔ 2NO2 (g)
C + 0.250 + 0.125 -0.250
(mole ratio)
E 0.250 0.125 1.75
Example 3 – A certain amount NO2 (g) was introduced into a 5.00 L bulb. When equilibrium was attained
according to 2NO (g) + O2 (g) ↔ 2NO2 (g) the conc. of NO was 0.800 M. If Keq = 24.0 how many moles NO2
were originally put into the bulb?
I 0 0 X
2.479 = x – 0.800
x = 3.279 M
Keq = [SO3][NO]/[SO2][NO2]
3.5 = (x)(x)/(0.80 – x)(0.80 – x)
1.87 = x/(0.80 – x)
x = 0.52
[SO3] = [NO] = x = 0.52 M
[SO2] = [NO2] = 0.80 – x = 0.28 M
Example 5 – 1.0 L vessel contained 1.0 mol SO2, 4.0 mol NO2, 4.0 mol SO3, & 4.0 mol of NO at equilibrium
SO2 (g) + NO2 (g) ↔ SO3 (g) + NO (g). If 3.0 mol SO2 added to mixture what will new conc. NO be?
Keq = [SO3][NO]/[SO2][NO2]
Keq = (4.0)(4.0)/(1.0)(4.0)
Keq = 4.0
Keq = [SO3][NO]/[SO2][NO2]
4.0 = (4.0 + x)2/(4.0 – x)2
2.0 = (4.0 + x)/(4.0 – x)
x = 1.33
Example 6 – Keq = 49. 2NO (g) + O2 (g) ↔ 2NO2 (g). If 2.0 mol of NO & 0.20 mol O2 & 0.40 mol NO2 are put in
2.0 L bulb, which way will the reaction shift?
(not asking for a #, no need for ICE; calculate numerical value of the eq. Expression
when system not at eq. → called Ktrial or Q; compare Ktrial & Keq)
Entropy: measure of disorder (chaos, randomness); greater the disorder, greater the entropy
(high entropy) gases > solutions > liquids >solids (low entropy)
- - equilibrium state
(temperature dependant)
+ +
+ - no rxn. (non-spontaneous)
In general ∆S>0 (+) when:
-liquids or solutions are formed from solids
-gases are formed from either solids or liquids
-the # molecules of gas increases during a rxn.
-the temp. Of substance increases
Solvent – a substance that does the dissolving. It dissolves the solute. Present in greater quantity
Solute – a substance that gets dissolved. Dissolves in a solvent. Present in lower quantity.
Solution – solute(s) + solvent creates a solution
Electrolyte – a solution containing ions which will conduct electricity
Dissociation – when ionic compounds are ‘pulled apart’ into their ions as they dissolve
Saturated – when a solvent can no longer dissolve any more solute
Unsaturated – a solution that could still dissolve more solute
Concentration: how much solute is in a litre (or other volume) of solution
Molarity: most common way of expressing a concentration (mol/L)
concentration example:
What is [Cl-] if 15.0 g CuCl2 dissolved in 100.00 mL of sol.?
CuCl2 ↔ Cu2+ + 2Cl-
15.0 g CuCl2 (1 mol/134.5 g) (2mol Cl-/1 mol CuCl2) = 0.2230 mol Cl-
[Cl-] = 0.2230 mol/0.10000 L = 2.230 M
Given a saturated solution of CaSO4,if another solution containing Ca2+ ions (or SO42- ions) is added, the stress
of additional Ca2+ ions (the “common ion”) will cause a shift to the left according to Le Châtelier’s Principle. As a
result there will be more CaSO4 (s) formed, therefore the solubility of CaSO4 is decreased.
The solubility of CaSO4 can be increased by causing the system to shift to the right. This can be done by adding
a substance that will cause the precipitation of Ca2+ (or SO42-).
Example: addition of NaOH. The OH- ion precipitates (is of low solubility) with Ca2+ causing a shift to the right