review reaction mechanism br 2 (l) step 1 br 2 2 br. h step 2br. + step 3 c 5 h 11. + overall br 2 c...

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Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br . h step 2 Br . + step 3 C 5 H 11 . + overall Br 2 C 5 H 12 HBr + C 5 H 11 . Br . C 5 H 11 Br + C 5 H 12 (l) C 5 H 11 Br(l) + HBr(l) + C 5 H 12 C 5 H 11 Br + HBr

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increase [react]  bimolecular elementary steps increase rate of reaction increase T  increase rate of reaction increase number of collisions increase force of collisions

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Page 1: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

ReviewReaction mechanism

Br2(l)

step 1 Br2 2 Br.h

step 2 Br. +step 3 C5H11

. +

overall Br2

C5H12 HBr + C5H11.

Br. C5H11Br

+ C5H12(l) C5H11Br(l) + HBr(l)

+ C5H12 C5H11Br + HBr

Page 2: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

Br2(l) + C5H12(l) C5H11Br(l) + HBr(l)

step 1 Br2 2 Br.h

step 2 Br. +step 3 C5H11

. +

C5H12 HBr + C5H11.

C5H11BrBr.assume step 2 is rate determining(slow)

rate = k2 Br.= intermediate[Br.][C5H12]Keq =

[Br.]2

[Br2]

[Br.] =

rate = k2 k’[Br2]1/2 [C5H12]rate = k’[Br2]1/2 [C5H12]11/2 order reaction Keq

1/2 [Br2]1/2

Page 3: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

increase [react]

bimolecular elementary steps

increase rate of reactionincrease T increase rate of reaction

increase number of collisionsincrease force of collisions

Page 4: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H
Page 5: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H
Page 6: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

minimum energy required for reaction:

activation energy

T1

T2

Ea

# molecules

Kinetic Energy

T2 > T1

= Ea

Page 7: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

Arrhenius EquationT dependence of a rate constant, k

k = k a) increasesb) decreasesk

R = gas constant (8.314 x 10-3kJ/K mol)T = temperature (K)z = collision frequencyp = steric factor (<1)

with Tz p e-Ea/RT

with Eaa) decreasesb) increases

Ea = activation energy (kJ/mol)

Page 8: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

p = steric factor

z = collision frequency

combine to give A

k =A e-Ea/RT

Page 9: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

Arrhenius Equation

k = A e-Ea/RT

ln k =y = m x + b

ln (k2/ k1) =

plot ln k

- (Ea/R) (1/T)ln A- (Ea/R) (1/T) + ln A

v.s. 1/T slope = -Ea/R intercept = ln A

(Ea /R) (1/T1 - 1/T2)

ln K = - (Ho/R) (1/T) + So/R

Page 10: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

A-B + C

A + B-C

A...B...Cactivated complexP.E. is at a maximumtransition state

Page 11: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H
Page 12: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

A-B + C A...B...C A + B-C

P.E.

Reaction coordinate

Eaf

Eab

Hrxn

reactants

products

activated complex

looks like species closest in energy

Eab - Eaf = Hrxn

Page 13: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

P.E.

Reaction coordinate

Eaf

Eab

Hrxn

reactants

products

activated complex

exothermic Eab Eaf>

endothermic

Page 14: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

products

reactants

Eaf

Eab

P.E.

Reaction coordinate

activated complex

exothermic Eab Eaf>

endothermic Eab Eaf<large Ea = slow rate

Page 15: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

- catalyst + catalystlowers Eaf lowers Ear

Keq unchangedand H

faster forward reaction ( kf )faster reverse reaction ( kr )

kf kr

= Keq

Page 16: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

Br2(l) + C5H12(l) C5H11Br(l) + HBr(l)

Hrxn

Reaction coordinate

P.E.Br2 + C5H12

C5H11Br + HBr

Hrxn < 0

Ea

Page 17: Review Reaction mechanism Br 2 (l) step 1 Br 2 2 Br. h step 2Br. + step 3 C 5 H 11. + overall Br 2 C 5 H 12  HBr + C 5 H 11. Br.  C 5 H 11 Br + C 5 H

P.E.C5H12

+ Br2

C5H11Br + HBr

step 2 Br. + C5H12 HBr + C5H11.

step 3 C5H11. + Br. C5H11Br

2Br.

+ C5H12

HBr + C5H11.

+ Br.

Ea

Ea Ea

Br2(l) + C5H12(l) C5H11Br(l) + HBr(l)h

step 1 Br2 2 Br.h

Hrxn