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Lecture 2
It is possible to describe
reaction mechanism by
using information about
reaction rate.
Chemistry, the Molecular Nature of Matter and Change, 7th ed.
A→B
Products (B)
Reaction:
Reactants (A)
Product (B) concentration increases ↑
∆𝑐 𝑐2 − 𝑐1
𝑣= =
∆𝑡 𝑡2 − 𝑡1
0 0.0100 0 0
50 0.0079 0.0021 0.0011
100 0.0065 0.0035 0.0018
What is wrong
with the
obtained
result? ∆ 𝑁𝑂2 𝑚𝑜𝑙 −5
𝑚𝑜𝑙
𝑣𝑎𝑣 =− = − −0.000028 = 2.8 ∙ 10
∆𝑡 𝐿∙𝑠 𝐿∙𝑠
𝑚𝑜𝑙
−0.0026
0,0075
𝑣𝑖𝑛𝑠𝑡 = − 𝐿 =
110𝑠
Concentration, mol/L
𝑚𝑜𝑙 𝑚𝑜𝑙
0.005 − 0.0076
=− 𝐿 𝐿 =
160𝑠 − 50𝑠
−5
𝑚𝑜𝑙
= 2.4 ∙ 10
𝐿∙𝑠
0,005
c2 − 𝑐1
𝑣𝑖𝑛𝑖𝑡 =
𝑡2 − 𝑡1
t, s
1 ∆𝐴 1 ∆𝐵 1 ∆𝐶 1 ∆[𝐷]
O2 𝑣=− ∙ =− ∙ = ∙ = ∙
𝑎 ∆𝑡 𝑏 ∆𝑡 𝑐 ∆𝑡 𝑑 ∆𝑡
Rate
K units: 𝐬
−𝟏
Concentration
Second-order reactions: 𝑣 = 𝑘 𝐴 𝐵 𝑜𝑟 𝑣 = 𝑘 𝐴 2 A + B → C + D
𝑳
K units:
Rate
𝒎𝒐𝒍∙𝒔
Concentration
Rate
𝒎𝒐𝒍
K units:
𝑳∙𝒔
Concentrations
aA + bB + … → cC + dD + …
𝑣=𝑘 𝐴 𝑚 𝐵 𝑛…
Reaction order: z = m + n + …
Both reaction rate constant and reaction order are not to be calculated empirically.
The exact values can be detrmined only experimenatlly!
• First-order reactions
Decomposition of nitrogen(V) oxide: 2N2O5(g) → 4NO2(g) + O2(g)
• Second-order reactions
Formation of hydrogen iodide: H2(g) + I2(g) → 2 HI(g)
t = 0s t = 10s t = 20s
λ
CCl2F2(g) → CClF2(g) + Cl(g)
Decomposition of car
exhaust gases
Usually large molecules of complex size and structure. Designed to be able to catalyze one
particular type of reaction.
Initially, nitrogen dioxide forms from nitrogen tetroxide. After an increase in NO2 concentration, also the backward
reaction begins and the reactants - N2O4 - are formed again. The equilibrium is reached when forward and backward
reaction rates become the same and the concentrations of reactants and products remain unchanged.
aA + bB ↔ cC + dD
𝒄
𝑪 𝑫𝒅 Kc – reaction equilibrium constant
𝑲𝒄 = 𝒂
[C] – molar concentration of product C, mol/L
𝑨 𝑩𝒃 C
– coefficient in the chemical reaction before product C
𝑨 𝒂 𝑩𝒃 𝟏
Backward reactions cC + dD ↔ aA + bB equilibrium constant: 𝑲′𝒄 = = 𝒄
𝑪 𝒄 𝑫 𝒅 𝑲
𝑪 𝒄 𝑫𝒅
aA + bB ⇄ cC + dD 𝑲𝒄 = 𝒂
𝑨 𝑩𝒃
𝑨 𝒂 𝑩𝒃 𝟏
cC + dD ⇄ aA + bB 𝑲′𝒄 = 𝒄 𝒅
= 𝒄
𝑪 𝑫 𝑲
𝑪 𝒏𝒄 𝑫 𝒏𝒅
naA + nbB ⇄ ncC + ndD ′′
𝑲𝒄 = 𝒏𝒂
= 𝑲 𝒏
𝒄
𝑨 𝑩 𝒏𝒃
𝑪 𝒄 𝑫𝒅
aA + bB ⇄ cC + dD 𝟏
𝑲𝒄 = 𝒂
𝑨 𝑩𝒃
𝑬 𝒆 𝑭𝒇
cC + dD ⇄ eE + fF 𝟐
𝑲𝒄 = 𝒄
𝑪 𝒅𝒅
𝑪 𝒄 𝑫𝒅 𝑬𝒆𝑭 𝒇 𝑬𝒆𝑭𝒇
aA + bB ⇄ eE + fF 𝑲𝒄 = 𝒂 𝒃
∙ = = 𝑲 𝟏 ∙ 𝑲𝟐
𝒄 𝒄
𝑨 𝑩 𝑪𝒄𝑫 𝒅 𝑨𝒂𝑩𝒃
Kc ≠ Kp
𝐾𝑝 = 𝐾𝑐 𝑅 ∙ 𝑇 ∆𝑛𝑔
= 𝐾𝑐 0.08206 ∙ 𝑇 ∆𝑛𝑔 , where T – temperature, K
Δng – the difference between the number of
gaseous molecules (products-reactants)
11.09.2018. Ķīmi1055: Ķīmija I, Mag.chem., researcher L. Buša 35
Heterogeneous equilibrium
Substances in the reaction are in different states of matter.
CaCO3(s) ⇄ CaO(s) + CO2(g)
H2 I2 HI
Initial concentration (mol/L) 1.00 2.00 0
Change of concentration (mol/L) -x -x +2x
Equilibrium concentration (mol/L) 1.00-x 2.00-x 2x
𝐻𝐼 2 2𝑥 2 4𝑥 2
𝐾𝑐 = = = = 50,5 4𝑥 2 = 50.5(𝑥 2 − 3𝑥 + 2) 46.5𝑥 2 − 151.5𝑥 + 101 = 0
𝐻2 [𝐼2 ] (1.00 − 𝑥)(2.00 − 𝑥) 2 − 3𝑥 + 𝑥 2
Equilibrium concentrations:
−(−151.5) ± 151.52 − 4 ∙ 46.5 ∙ 101 𝑥1 = 2.32
𝑥1,2 = 𝒙𝟐 = 𝟎. 𝟗𝟒
2 ∙ 46.5 [H2]=0.06M; [I2]=1.06M; [HI]=1.88M
11.09.2018. Ķīmi1055: Ķīmija I, Mag.chem., researcher L. Buša 37
Le Châtelier’s principle
When any system at equilibrium is subjected to change in concentration, temperature, volume, or pressure,
then the system readjusts itself to counteract (partially) the effect of the applied change and a new equilibrium
is established. Effect of pressure change
Effect of a catalyst
Effect of temperature change
The addition of a catalyst does not affect the
equilibrium, it only accelerates the reaction speed As the temperature rises, the balance moves
- the equilibrium is reached faster. towards the endothermic reaction, but, lowering
the temperature, towards the exothermic reaction.
11.09.2018. Ķīmi1055: Ķīmija I, Mag.chem., researcher L. Buša 38