Part 2.

Surface phenomena
Chapter 4. Surface phenomena & Adsorption
25.4b hien dung dien tich

A monolayer of CO molecules (effective area 0.165 nm2) is adsorbed on the surface of 1.00 g of an Fe/
Al2O3 catalyst at 77 K, the boiling point of liquid nitrogen. Upon warming, the carbon monoxide occupies
4.25 cm3 at 0°C and 1.00 bar. What is the surface area of the catalyst? · tinh dien tich be mat chat
S

~ the tich Co
hap phy Xeis fac

Bu 1 : int somol Co
bi hap phy
CO

PV
* R = 0 082 L atm/mol K
McgRT , . .
=
L

10 " F/AlzOs
=
No =
PV
=
1 4 25
.
, .

=
1
,
0905 .
10 mol
RT 0 , 082 . 273

Bur2 : xai dink so phan tu Co

N
1
=
neo . Na =
1 , 0983 .
10-4 .
6 02
,
.
10 = 1 , 1429 .
1820 (molecules)

Bu 3 : finh ting dien Hich be mat be phi bi Co

I

Vimoi phan fu CO chim 0 163

,
nmiz

= So = Nco .
Aco = 1 , 1429 .
1820 .
0 , 163 = 1 0830
, .
181 nm2
= 18 ,
838 m

Cách 2 :
25.9b
A certain solid sample adsorbs 0.63 mg of CO when the pressure of the gas is 36.0 kPa and the
temperature is 300 K. The mass of gas adsorbed when the pressure is 4.0 kPa and the temperature is
300 K is 0.21 mg. The Langmuir isotherm is known to describe the adsorption. Find the fractional
coverage of the surface at the two pressures.

0, 63 O =
my =
my
1 kP
Pl = 36RPa +

Mc =
, 21
0
my
0
Pz = 4RPa => kP =

I-G
T = const

=>
Pl (1 -01) =
36 9
= =

P2 (02/1-02)4

<
A M =
=

0 Re

S
= >
ti =
0 , 75

02 =
0 25
.

25.4
The data below are for the chemisorption of hydrogen on copper powder at 25°C. Confirm that they fit the
Langmuir isotherm at low coverages. Then find the value of K for the adsorption equilibrium and the
adsorption volume corresponding to complete coverage.

form of Langmuir isotherm

1

&
Linear P P in which 1
y x
: : =
;
=

= +

V Kum Un
adsorption capacity

=
y = a + bx

& -msm
& =03As a pa
mode 6 =

2 = a = 629 , 13
↓

OPTN 4 b = 1
,
7667

r = 0
, 9974
25.5
The data for the adsorption of ammonia on barium fluoride are reported below. Confirm that they fit a BET
isotherm and find values of C* and Vm.
(a) θ = 0°C, Po = 429.6 kPa:

ly
↓Po
P P atbla
<
y =

;
x = =

& S
c 1
, 1992
0 0 0761
-

a= =
,
= ) *
b = 0 , 0761 Vm .
c

9977 Po
n= 0
, = . 1992
0
*
Vm . C

S vm 13 , 070 cm3
=
= )
*
C = 164 , 07

~
phaixas dinh 22 =
xinh mi hinh phi hap
&

(b) θ = 18.6°C, Po = 819.7 kPa:

S - 00793
S0
a = 0 2489 =
,

b = 0 . 0795 m
2 = 0
, 9997 = 0
,
2489
y

25.7
The adsorption of solutes on solids from liquids often follows a Freundlich isotherm. Check the applicability
of this isotherm to the following data for the adsorption of acetic acid on charcoal at 25°C and find the
values of the parameters b and n.

wa is the mass adsorbed per unit mass of charcoal.

 => In Wa = Inb +
1
In C
N

in which :
y
= In wa = x =
(nc(y = a + bx)

S (n
a =
- 1
,
8264 = 443

= b = 0 , 43 =

1 = 0 , 9986 In b =
=
1 8264
,

~
=

(n b
=

=
2 2
,

, 16
0

25.9‡
A. Akgerman and M. Zardkoohi (J. Chem. Eng. Data 41, 185 (1996)) examined the adsorption of phenol
from aqueous solution on to fly ash at 20°C. They fitted their observations to a Freundlich isotherm of the
form cads = 𝐾. 𝐶𝑠𝑜𝑙1/𝑛, where cads is the concentration of adsorbed phenol and csol is the concentration
of aqueous phenol. Among the data reported are the following:

Determine the constants K and n. What further information would be necessary in order to express the data
in terms of fractional coverage, θ?

Cads = K . = Incads = Ink +

1 Insol in which :
y
=
Incads = In
(y = a + bx)

(in1k \VFOB
= - 1 9073
,
= =

=
1
,
716

In order to find O ,
we need to have the information of Cads max

25.11‡
M.-G. Olivier and R. Jadot (J. Chem. Eng. Data 42, 230 (1997)) studied the adsorption of butane on
silica gel. They report the following amounts of absorption (in moles per kilogram of silica gel) at 303 K:
Fit these data to a Langmuir isotherm, and determine the value of n that corresponds to complete coverage
and the constant K.

P 1 P in which :
y
p x p
(y a + bx)
= ;
= =
= +

M k .
n N

I & !
=
a = 24 , 641 = 0, 1731 n = 3 777
,
=
)
b = 0
, 1731 10
~ = 24 , 64 = k = 7 0249 .
,
2 =
, 99/2
0

25.12‡
The following data were obtained for the extent of adsorption, s, of acetone on charcoal from an aqueous
solution of molar concentration, c, at 18°C.

Which isotherm fits this data best, Langmuir or Freundlich?

P P
Apply Langmuir : = +

M k .
n N

(3
C1
=
> = + a = 33 6264
,

S K S S
.

= 0
, 1620

0 9734
r =
,

Apply Freundlich
1 Inc
: In s = Inb +

&
) a
=

- 1 9731
=
,

b = 0 3392
,

n =
, 9999
0

Freundlich isotherm the data best

=
Freundlich Langmuir =
fits
25.31
The designers of a new industrial plant wanted to use a catalyst codenamed CR-1 in a step involving the
fluorination of butadiene. As a first step in the investigation they determined the form of the adsorption
isotherm. The volume of butadiene adsorbed per gram of CR-1 at 15°C varied with pressure as given below.
Is the Langmuir isotherm suitable at this pressure?

Investigate whether the BET isotherm gives a better description of the adsorption of butadiene on CR-1. At
15°C, Po (butadiene) =200 kPa. Find Vm and C*.

S
= a = 0 6639
,

b = 9 94 18-3
,
.

r = 0
, 9999

& =OS
= -I s
 Part 3. Reaction rate &
molecular kinetics
Chapter 5. Reaction rate

a) True False (Complex or

non-elementary reactions do not have a well-defined order
b) False : The dimensions of the rate constant depend on the overall order of the reaction

c) True

d) False

e) True :
According to the Arhenius equation :

2) True False (negative orders mean that an increase in the concentration of a reactant can decrease
the nate)
g) Tre : Rate constant (h) represent the proportionality factor in the rate law

h) False : in the rate law , there can be the

appearance of catalysts and intermediates

a) first-order h(s) : b) second-order :

h(s"mol ! L)
c) third-order :
R(smol ? (2)

3,-1 (back)
-

a)k = 1 73
, .
10 PV = nRT

R = R . [N20s] => 0 1
,
.
12 = n .
0 , 002 .
298 = n = 0 049 mol
,

V = 12dm = 12 = [M0s] =
n
=
0, 049 4 09 103M
= , .

V 12
0 , 1 atm
PNOs =

T = 25 % =
298k R = k . [N20s] =
1
,
73 .
183 .
4, 09 .
10 = 7 073
,
.
10-0 (mol (15)
.

5 8
107(mol 5)
-

R = =
5 = 7 075 10 .
12 = 0 , 491
,
. .
.

b) 2N20g <
4 NO2 +
O2
=> R =
- 1
.
d[NOs]
2 dt
 =
d[NcOs) -

2R =
-

2 7 075 10-0 = -1 413 187 (mol ( 5)

= . .
,
. . ·

dA
d[NOS]
c) number of molecules decomposed per second =
.
V . NA
dt
7
1823
-

= 1 415
, .
10 .
12 .
6 , 022 .

= 1 023
,
.
1018 (molecules

d) N2Os 2NOz +
1
<

halved R dINOs] 10-8 107 (mol (5)

As the coefficients is = > = -
=
2r = 2 7 073 .

,
.
= 1 , 415 . .

dt

=>
J' = 25 = 2 8 , 491
. .
10-7 = 1 6982
, .
10's (mol =) .

k
3
3 46 10
3
(59)
-
-

=> = 2k = 2 1 73 00 = .

,
.

,
.

2A + 2B -
2) + 2D

2C F => Overalmxn : 3B > 2D + G

F + B 2A + G

&
reactants : B ; products : D
,
G

= 3 intermediates : C
,
F (dis tao na
xing mat di)
catalysts : A (sau pi phai cinnguyen mat dixing supe tao ra)

R = 2 .
18" (L mol-5)
.
=> second order reaction
 A , B > C

a) [A] = -

[B] : False :
Concentration can't be negative
b) ATA) = -

AIB] : False

(su mut diaiu A =

sutang (inciuB) X

si met diain su mat diain B

= A =

c) A[A] =
A[B] =
A[C] :
True Đây là biểu thức thể hiện sự bảo toàn khối lượng (giả sử tỉ lệ phản
ứng là 1:1:1). Khi A bị tiêu thụ để tạo thành B, và B tiếp tục tạo
thành C, tổng sự thay đổi của các chất trong hệ vẫn giữ nguyên.

,
di phan hig 35 %

=
> ciulai63 % =
[A]tai this diet
[A] ban dai

9)
IntAS -Ret In (0 63) R 323 k 1 323 10
= -

= =
= = , .
.

Ra = 2k = 2 .
1 , 323 .
18
3
= 2 , 659 .
103(st)

b) In 70 % complete In (0 3) 18-3 +zo (s)

=
,
= - 1 323
, . ·
=
fro = 900 33
,

3
fa complete (0 1) > (s)
-

90 % = In ,
= -1 325
,
.
10 ·

+go % =

goz
= 1737 , 16

3
Prob .
16 5.
<k = 1 73 10
, .

3(s-1)
-

3 , 46 10
a) ka = 2k = .

first-order reaction

In=
·
In2
tr A = =
20033 , 13551
,

3 46
,
.
18-3
b) In [NO3]ann = -RA .
t

[NzOs]o
In [MOs]24n [NOs]24n do
"
=> =
-

3 46
, .
10 - 3 .
24 3600 .
=c = 5 0316
, .
10- mol .

, 01
0

a) 2NOz + F2 >
2NO2F
k = 30dm? Mol 5' . .
=> second-order reaction

[NO2] = 3 10 - 3 M [F2] =
7, 3 10 M
=
.
; ,
.

[A] [NOc] 10 - 2 73 10 + 2. I
[A]o
- [B] + [B]
=
. =c = 3 .
.
.

btAJo IEBJTBo
[F2)/7 3 10
#
= R T In , .

= 38 10 ②
3
.

2
.7 5 , .
00" -

5 10.
-

[NO2] 3 10.
3

S &
insent fo [F2] 0 , 003038 mol
> Fz
= =
= 2 015
,

[NO z] = 0 000076
, Ma = 0 , 0304 mol

[NO , F] = 5 .
10 - -

0 , 000076 ↑
Nof
= 1 9696
,
mol

b) Rt = 0
= R .
[NO2]o [F] o .

= 38 3 .
.
10-3 7 , 3 10-3 . .
= 1
,
423 .
103(L molts) .

R
+ = 10
= k .
[NO] [E] .

= 38 0 , 000076
. .
0 , 003038 = 1 , 455 . 10-3(L .
mol ! 5)

-MIA
dIA)
R =
-

=
-[A] =
# -RA In

"+ 1 n+1
[A] :
-

= A =
-

[A]

R( - n + 1)
While [A] = 0 = c < 0 (= -
n + 1) &

= n

"
b)
2
a) Re =
RIA) [B] R, = RIA] [B]
R2 = R .
2, 2 STA) ? 3 [B]
.
= 6
, 75 Ri R2
=
27 = (3[A])" -
3" =
27 = n =
3

Ri [A]"

a)
In (l-1) In[ASo In (n-14 * [A] 1. [A]
tyq
= =
.
-

qn - 1 9

1
=

>q = 0
,
69 = 1
,
45

- Intagg =
(l-n)In[A]o-In (n-1) . R
Cy = bx + a) with
y
=
Intog ;= In[A]
-1
1
,
49n -

&
=
a = 4 256
,

b - 0 4426
=

,
= 1 -
n = n = 1 4426
,
 (n(n 1) k In(1 4426 -
1) k 0 9329
4 256 ,
k
- .
.

a = -
= = -
=
=
,
,
4426 1
49n
1
431
-

,
-

1, -
1 1, -

"" "
b) [A] =
1 + [A] .
(n-1) RA .
t 16 28 .

[A]

1 1 4425 4423
[A0]0
-

,
,

=
0
,
69 = 1 + .
0 , 4423 .
RA .
t

=A 0 , 4033
=

[A0]94423t
=
>

&A 3 75
,
.
183 3 63 183 3 77 183 3 69
,
103 =
Ra = 3 715
,
153 SAI
,
. .

,
. .

saA + bB ,
products

[B]

[HyBi] j
=
39 , 3 mmol dm3

In iBo
[B]/[B]
I
·
In ·
- = =
m .
alo-b IAt lua
b [A] [A] [A]
a
. [B] o -

.
·
o

393mmoldmY =A
also have
:AJO-B
we =
= OO

6
,2
ATA] AlB] 4
= =

. 1 9.
7,98

#159
3 133 3/29 2/19 319 . .
. . ,
7
 /gs k 9 . 2127 .
183
127 .
18

= =

96 , 6 .
10 -
39 5 .
183
,

=
1
,
6134 .
183 (molL St) .

*
Trag pha Phi ning dotis le ,
than va

apsuct khi co dinhas ye t Rhi

1 :
X dink
I
bas pi
phabac v bac this
ko O vi : O
gian tany
-

I /
,

bao nhierlan giam bay nhieu

thining do ap zit se
-
test bacl :

In [A]A =
-

Ra .
t
(y =
bx)
[A]

(ka
= =
4 , 1762 .
183

2 = 0 9361
,

= n2 = 0
, 9141 (loai do tha thap)

1
-
test bac2 :
-
1
= RA .
+
(y =
bx)
[A] [A]
0 4222 100 (stat) 00314(2 mol" 3)
(kA
= = = 0
, ,
.
. .

r = 0
, 9717
= 22 =
, 9442
0 (nhan--)

- latm = 760 for v P = C R T

.
.

=> Ifon
= ! atm =
Mo .
0 , 082 .
(326 273)+

760
 "
= =
760 R . .
Th
tar mul

=
O

=m
Ro Re Rs R4
?

<
a) R = R .
[A]d [BJP .
.... []

we have :
R2 = -
0 . 64 03 ? 00 =
34 =
101 = = 1
R, R 0 2
,
0, 3 0 . 15 0 60
,

R30 , 15
0 0
, 60
= B = 2

34 39 %
&
38 - No
M 0
.
0. 043
- -

Ra 0, 6 0
,3 0
, 13

b) Ro = R .
[A] [BJP .
[C] ,
,6
0 10-2 G
27
.

= 0 6
,
=
k .
0
, .
0
,
32 .
0 , 15

k (2
= = 0 , 3333

mol ? S

C)
 120 120 128

69 139 277

In exp1 : [A] [B] = [A] dinin Re

R =
-
d[B] d[C]
=

dt at

(IBS- 4 10-4)
104
=>
-

.
2 . [B] = -2 .
10
_

120

prbas
"
[B] 0 [B] bigian 1/2 +xz const 1
-

4 10. => => = 120s =

=

=
=
R =
Ry[B]

In exp2 : [A] <[B] => [B] di ninke

R =
-
d[A] d[C]
=

d dt
-

([A] -4 10-4) .
2 .
10-4 [A] = -
2 18-4
= = = .

69 .
183 69 .
103

[A]. = 4 .
18-4 =c [A] bi giam // hang Rhi +
Tang gp di (69-139) =
yz va[A] , tylnghich
=
pi bas 2
<
= R =
RAIA]
= R = R . [A] ? [B]
In 2 (n2 (st)
viR =
RB [B] . = R =
= =
0 003776
,

+2 120

RA 1
03623((4mols]
Ra [A] "
1034
R = = =
=
0,

Cao"
.

t
12 .
69 . .
104
 a) False True

b) True

a) Twe
b) False

RI P2 R3 M4

a)
R = m .
[C0-]" [I-J ! For -]
.

Rp = .
[Co -J , [I-3 , [OH-] ,
R2 4 18-36 03 = b= 1 =
0 48 10 - 3 = R 4 10-3 2 18-3 1000 18
,
.
= - .
.
. . . . .

Ry 2 .
103 0
, 24
=
k = 60 (4molds (s) ?
C
Ry 1008 0
, 24 = C = 1
= =

1
R4 250 , 94
0

=
a
RI
=
4 I
2 040-a =

R2 2 4
12/mol ?.
0. 3
?= s

= R = R .
[00-] [I -] [OH']
. .
3) Gaycchepu phihip v phinhtd -
* Giaithich
(1) .
20
-

+ 04 - = HOCK- (nhaun) (1) .

= k =
[HOC2] = [4022) = k .
[00-] · [ou']
(2) .
HOU + 1
- -

> Ol- + c
(cham) [Co-][oH]
(2) .
= r =
k .
[HOU2] [I] .

=
R K . . [U0] [OH] [I-] (thoa
·
rate law)

d[Oc]
9) = 242 [0] [Os]
.
.
+ Ro [Os] [M]
.
.
-

R
_
p
. [02] [0] [M]
.
.

dA sinhea : + R .
What gi mui tin)
* Cach ghi :
quantam O sinh ra/tiently dan fieuthu : -K .
[chat gimi tin]
d[Os] Rp [0s] [M] [02] [O] [M]
< =
-

. .
+ k
...
. .
-

Re [O][on]
.

dt

b) Steady-State Approximation
(gia dink ning to wa chat
bung gian gan nu ko thay di theo the gian)
I

d[Intermediate] =
O

dt
 d[0] [82] [0] [M] R[0] [Os]
= Ro [0s] [M]
.
.
-

M
...
.
.
-

·
=

dt

=> R [Os] [M] = R [O] [0] [M] R2[0] [Os] +

...
. . .
. .

d[O2]
=> = 242 [0] [Os] .
.
+ Ro [Os] [M]
.
.
-

R
_
p
. [02] [0] [M] .
.

dA

= 242 [0] [0s] .

.
+
R · [0] [0] [M] + R2[0] [Os] .
. .
=

R
_
p
. [02] [0] [M]
.
.
=
3 Rz [0] [Os]
. ·

d[Os] Rp [0s] [M] [02] [O] [M]

=> =
-

. .
+ k
...
. .
-

Re [O][on] .

dt

. [0] [0]
R [M] R2[0] [Os] + k [02] [O] [M] R TOTTOs] =
2Rc[0] [Os]
- -

=
- -

...
. .
. . . .
.

2) Bri2 tao
1 do t RIO][O] RI]
19 202 = R = .
= .
2 .
=

[0] =
R , [03] [M] .
> chi'xet hang pe 2
m
_
[02] [M] .
+
k2[83]

RLOs] [M]
Ry [03].
GOs)
= R = .
.

4 [02] [M] .
+

d) Equilibrium Approximation
(Gia sink
·

rangmat
bu phan ung dautin xayra rt nhanh va dat can
bing ngay lpts
vd : A + B -
C (nhank)
m
C + D
R2
products (cham) *

=>
Keg =
TOSIMSISTOSR = Ross
R 1 [02]

R = kz [0) [On]
. .

= KIRz[On]"
k - [02]
 (SSA) (EA)
no thi ?
e) Hin kien steady state -eq approximation
KhiSSA-EA d[intermediate) this
O = ding per dat can bang
d

bu I vis nhanh vin c chieuthuan va coter do gan bang nhau

=
!
nghich
=> RLOs] .
[M] =
R_p [02]·

.
[O] [M]
.

Xacdinh san pham hung gian NOs No :

-
,

2
Apdung pluing phap ning do in dink
demo- ;
ano-o
tim hin
3
phung

+Ra:CNUSTR-anonSer
+ &(Noz =

at

= O

do Rb (No Con-Mc CN No
+ =
.
. .

4 bin di (No (no thank ham theo reactants

, , products =
G

Choco intermediates)
(No =
Rb . (NO
kc

Ra CN20s
.
-

M-a (No .
·
Coy- 2kb (No (Noz ·
= O

=
(No
=
Cn Cao
3 Tim phing Link to do phan eng
*
Chan O2 defin (vi it tham gia vao cas pi Lung gian nhat)

&Coz Ra CN20s Ra Rb R
R +
Ry (No <Nos + Rb (NO2 CNOs CN2Os
.

=
=
+ =
.

=
=
. · .
. · .

1dt
(k -
a
+
2kb) (No
.
(m -
a
+
2kp)
 -

in (16 60)
[ho IO]
=
Re
.
:
Key =
= =

R -
1

do =
1
R 2 RENOS .
=
.
.

=
RoRz [No] ? [O] =
R: [NO]"[O2]
R -
1

in (16 61)
.
:
Keg =
R
=
[Nob]
=> [Nos] = .
[NO] [02] .

k -
1 [NO] [a]
.
k -
1

R =
. dENO]
1 = G2 [Nos] [NO]
.
.

2
da
=
Rekz [Nos ? [Or]
.

=
R . [NO]"[O2]
k -
1

in (16 62)
.

Celementary reaction) =
phunghinh ter di 1
stri lay bus tipi phinh phan ti
tham gia -bac the NO bas 1 the O
= 2NOva 10
, wing 2
,

= R = R [NO] ? .
[O2]
2

a) The False . hang so

hang cangthic chi la de chuyen d din vi
/
thank 5/mol .
K

b) False . Anhenius equation chis

many y nghia di doan - co the co sai lich hang this te
c) False .
 & R 314 5/mol k
eFA/RT
= 0
,
.

Apply Archenius equation : k = A .

-
177 1838 ,
314 660
10-3
.
.

At 660K : 1,2 .
= A .
e

A =
1 2248 101
= ,
1038 314 728
.

-
177 , .

dmmol's-1
.

At 728k : k =
1 2240
, .
10% .
e = 0 0176
,

e-FA/RT (y a) with y Ink

A 3 bx + x
1
= = =
=
.
,

(2 mols)

& S
=
a = 24 , 8987 = In A =
A = 6 , 31 .
100 .
-

b =
-

19431 , 1034 = Ea/m Ea = 161350 , 2103 J/mo

n = -

, 9989
0

e-FA/RT Ea/8

&
314 780
-

18
, .

= A .
= (1) : 1 2
,
.
= A e . = C
Ea =
198193, 1277 Jimal
-Ea/8 , 314 629
(2) 18553 A 8710 18"L mols'
.

: 3 .
= A .
e = 1. . .

12 -Ea
bes
I
In =

700
=

3 0 , 304

= Ea = 190193 , 1277 J/mol

=
> A = 1 , 8710 .
10" Limol ! s

= AE (ni nany)
 AH = AU + PAV = AU + ART

= AU = AH-ANRT
=
-
393 31
,
+ 90 23
,
+ 198 33
,
-
33
,
18 -
0 = - 225, 91 h5/mo

Eagaward-Faback = Al

=
Faback = 116 + 225 , 91 = 341 , 91 RJ/mol

-Fo
a) T : 300k- 310k
=
In 6 . 5 =

R :
R = 6 5R
, ,

= Ea = 144728 ,
1187 (5/mol)
b) T : 300k > 310k -

Fa = 19kJ/mol In ke =
-19 1031 .
1
=
k2 =
1
,
2706

Re 0
,
314300 300 RI

vi'du

42 + Iz < IHI (elementary reaction) = >

day la bus quyit dinh t do per hein

=
stoichiomehic number = 1

(chi' can 1 bus de sinha san phane dung v he s phan ti nhu trong phan ung ting the
b)
-

ArGP/RT
kj = e
 2AgGCHI)-IAG
ArG =

= 2 (- 11 8) o
hang that chuan
.
,

=
- 23, 6k5/mol

=> ky = 91 2
,

(s 1)

- [M] total concentration of all

:
species present
have Po
we :
PVm =
nm .
RT => [M] =

RT

=B RT .
m 1
(16 85) > 1 (s) CyAta
=1
=
.
= +

Runi M .. R2 R [M] .

k-
8779 1428 1/k R2

=> =
a = =
,
.

** 60
b 182668 , 2998 =
RT/R (tm) ,
240
,
3330k a
.

0
, 9997 , 082
0

m
MT=42OSs
=

k k
+ 0779 ,
1428 = =
2223 , 3373

k ,. R kz
 diBic] =
-

k [Bez] [M]
.
.
+ R - p[Be] ? [M] -

Rg [H] [BL]
. .

dt

diBi] 26., [B] ? [M]

= Chi [BiS [M] .
.
-
-

R2 [B] [H] .
+
R-2[HB] [H] .
+ R
3
[4] [Biz]
·

dt

a) (1) : initiation

(2) ; (3) :
propagation
(4) : termination

6) overall reaction :
CH3CH0 <
CHp + CO

c) steady-state approximation :

diCr] =
Ro .
[CHCHO]-Ry[CHs] [CHCHO] Rs[CIy(O] - 2Rp [Chy]2 .
+
.
= 0
dt

d [CrsCO]
= R2 [Cr] [CryCH0]
. .
-

Ry [CryC0] .
= 0 = c
RICH][CRCHO] =
RICHy(O)
d

dicr] 2RpIcHa] Retracho]

=>
> = Mo [CCH0]
.
-

= 0 =
> RICH]" = &

df 2

* T
di phan ung dur guyet tink bi bus
( propagation (2) (3) ,

Nei R =
dICH4] = Rz [CL] [CrCHO] ·

dt

d[co]
Neu R = =
R
> [CrCO] = m
= [Cr] [CrCHO] ·

dA

& = [r] =
RECECHOS = >R =
Rz ·
Re
.
[HCHO]3
2k4 2k4
-

(3)
a) Initiation : (1) ; propagation :
(2) V; termination (3) : ?
b) Steps 1 and 2 each to be in
ey
ke
=
[S] [MS [a] = [C] =
RICh]
= =

R
- [C][M] [Cz] k -
1

he
=
[COU] - [COU] =]icO]
R k
-
2 [UJICO] -
2

dicoa]
= R2[c][coJIM] -

R_2[COU] [M] Rs[con]ICh] b -s [COCI][a]

-
+ = 0
dt

dIcoc [cod]
L
My =
= ,

Rich]
[CO]
= Ry R2 .
R .

· [ch]
k -
2

-did
RIC
c) Rb =
= m EOCS[C] =
Rs[COC]
k -
1

a) False
b) Tre

c) False .

d) False
Lineweaver [S] [CO 2]
=
(g = bu + a)

Burk [E] =
[BCA]

I
= a = 4736 , 4346

b =
39

n = 0
,
9996
1 4736 4346 k2 73402 , 9939(s 1
-

= = =
,

RLE]o
km
= 39 = km = 0 000234
, (mol (1)
.

RzLE]o

R = R .
[NH3]"

In ( + +2) = ( n)
-

In Po -
In (constant) (y = bx + a)

S
=
a = 0 , 6191

b = 0
, 9832 = 1 -
n = n0

n = 0
, 9999

9) False .
For both first and second under
b) Twe

c) True. Due to Anhenius

.

equation
 d) True·

e) True

1) False .
It
just true for reversible reaction
g) True .

Partial order : bas singphan .

vd : R = R .
[A]M[B]"
S

coefficients : hiso can

S
bang .
Vd : A + 2B -> C

reaction (lin lin ching phan and his fieje xas saf va cham
Partial under =
coefficient :
elementary do

air fing phanti

vd : NOz + 20 >
-
NO +
CO
R =
R . [Noz]2
= partial order = 2 + coefficient = 1

h) False the la
.
Partial order =
coefficient chia chas da
elementary reaction, co vofinh
i) Tre
j) False . R = A .
e-FA/RT
2) True .

1) la always
False .
Ro phai do en gan cui R se giam ,
conc per than nghich ,as tes,..

m) False

n) True ·
Nang Ling hoat ho lin
duing (Ea 0 his pi xay ra de hirkhi T
giam, hai vithi ti)
 >
zeno order reaction

= k =
, 00056
0 mol . -! s

*
hang ding ha phanlng , dao ham
di] chinn la d dis cua do thi [H) theo e

=
dir] =
-
0 , 00036

It

R = -
1 dims
- = 0 , 000107 mol .
(% s
-

3 It

B :
Catalyst
D : intermediate
A+ E - F + C

GlAJIB]
a) dID] = ReTAJIB]-RIJID]-ReID]lE] = 0 = c [D] =

at R [C] +
Rz[E]
d[F]
R =
= R2[D]lE]
It

-TASIS
b) first step is
ey =

>G =P [D
=SB
d[F]
R =
= R2[D]lE]
It

=
KIRz[AJIBS[E]
-, [C]
k
 bussing sang Xand : = 464 nm = 464 .
18-m Bl : Tickphoton hap thu
so

any luingcia 1 photon

Tinh he
sing sucit and sang ti = 0 00133 W & : E =

X
%
antsing bi hap phu = 74, 4 %

somol sen pham tao 106 mul do (plank const) 34J/

68 trong h 6 626
:

na : n =
,
.
: = 10
,
.

this gian chien 110s 108 m/s

sang : t =
c = 3 .

34
6 , 626 10 108 18-19 J/photon
-

3
= E =
.
. .

=
4, 28 .

464 10-9 .

Figmanyhywnhsahapt133W
&

.
74 4 % = 0 0011332w
, ,

Ting rang living hip thy Long 110s = 0 0011332

, .
110 = 0 126835
,

0 , 12683
& Sophoten hapthu =
= 2 96
,
.
10 photons
4 , 28 .
10-19

photon
Tinh reacted molecules
B2 :
quantum yield :
8

number of absorbed

(inhinsic)
* Mai photon tao
&
nu 1 Ho va 110 = Vi = 1

1 .
(photo dissociation) H·
fiep bus phan any HI tas them san phai
(chain propagation)
.
2 =>
fingHImat/photon = 2 = V =
2

3 . (termination)
~

intrinsic quantum
yield

9)
* Ja la somol photon hap the mor gig
:
then 1 dinvi the tich

Pe 1 .
tao la 14. va 1 I ·
cho ma photon hap thu
2
. gi Hotao them 1
-
I
bang cach lay Ho an HI detao He va I

= Miphoten hapthu can pha hig 2 HI

bri1 mat 141/photon d[HE)

3
R Ja - =
R= - = 25a
=

at
2 mat them 1H1/photon - R = Ja

Quantum yield (U) :

V =
reacted molecules
=
sophan tu HI bi phanhiy
=
2
=
2

number of absorbed photon sphoten hap thu 1

 1kcal = 10" cal = 4 184
,
.
1835 (fingang king hap thy)
230 nm = 250 .
18-m
ha 6 626 18.2 " 3 100 10 5/photo
3) &
Nangling 1 Photon E 7 9312
, .
.

= = =
,
.

X
250 .
18-9

4 , 184 103 Do photo

& Sophoton hapthu 5 , 2621
.

= = .

7 , 9312 .
18-19

& SoHl bi phan hig =

2xSphoton hap thu
1 0324 102 bei
=
, chan .

k, * Reversible >saut() , Agiam va

Bang
Ri
n B

hoci
&
As

A
A
①

[A]o = 1 mol/L ; [B]o = 0

a) Ry) br =
pithuan manh han pinghich
-

he singhieng veB fai that can being

= >
-
hang

S tasgiemmanh ratemcngiahithaa
=
·
S

b) ky =
kn =
puthuan nghich being nhau =
his can bing fai [A] [B] =

=
hai dung se staxing nhau vatiem can nhau tai dien gin =
 MX [A]o/2 Khi day li pi 1 china
=

C)
cir dayla per than nghich [x] = =
Ex30

10-
Panta : = > = Xx = 0o
,

0
, 90912 0
, 063
0 9091-1/2
In , (10 1) + 07239(s)
= 3 -
= + .

+z
=
+x =
0
,

0 9091
,

10 0 x0
Partb : =
+
=
Xx = 0 3
,

18 1 -
Xx

In 0 , 3 0 , 23
(0 + 10) +(2 0 035(s)
+
-

=>
-

= . = = ,

,5
0

Eg = 10s ; Re = 1s
1

0 , 9091-[BS
In Hermay [B] : In =
-

(10 1)
+ .
0 33
, = [B] = 0 8098
,
mol

, 9091
0

In term of [AS : [A) = [A] .

-

[A]pu = 1 -0 , 0098 = 0 0002

,
mol/

a)
b) ky > ke =
follow the hend of graph 1 and [A]o [B] =

Es
B
= >

1-

A
A
c)
=
10- Xa =
0 , 01

=>
In 0 , 8082-[B] =
-

(10 + 1) .
0 33
,
= c [B] =
0. 8 mol/L
0
, 8182 = [B] 0 35 =
[BJo [B]pu + = 1, 8 mol/L
,

also have [A]os [A]o- [ASpi

=
=
1-0 , 0 = 0 2
,
mol/

&2
Am , B ,
C At + = 10s :

-
0 , 01 10
[A]
.

= 0
,1 e = 0 09 M
.
.

[A) [A]
=
..
e-Bet [B] =
0
, 01
.
0
, 1(e
-9 , 01 .
10
-
e-01 .

10) = 0 006
,
M

, 1-0 , 01
0

[B] =
Re · [A]o(e-met-e-Ret) [C) = 0 1
,
-
0 09
,
- 0 006
,
= 0 004M
,

kz Ri
-

At + = 100s :

[c] = [A] .
-

[A] [B] -

[A] = 0 0360 M
, ;
[B] = 0 0041M
, ; [c] = 0 , 0391 M

molthu did this te

chieu suct phan tram toda =

mol to da cothes fao

fi chat die
 me
[CGCO] =
. (hAJo-[A])
kn + Rz

maximum yield = + = 0 = [A] = 0

ICOS - MAS = =
0 3342
,
= 3

initiation

propagation
termination
initiation

propagation
retardation * - Gi A :

bitiu nao
nhing ko to eu san phai
termination
cuci cring (P)

NO : intermediate

d[NO3]
=
B . [NLOg]- Ri .
[NO2]INOs]-RINOz][NOs] = 0

dt

= [NOs]
:Ho
his
hiOS has a
d[R] Pu [NOzS
M = = R [NOSINOS
. = .
=

dt .
 dINO]
= R [NO2] [NOs]-R , [NOSINOs]
.
= 0

dt

In a
= [NO] =

d [NO3]
=
B . [NLOg]- Ri [NO2]INOs]-R[NOz]INO S]-Rs[NOJINO]
.
=

dt

k , [M203] k , [M203] R[n283]

= [M8s] = = I

(hi + 12) [Noz]

.
+ R
> [NO] (hi + 12) [NO2] Ra[NO2]
.
+ (ri 2R2)ING)
+

d[02] ke [NOs]
↓
R =
= E2 [NO , ][NOs]
. =

dt hi + 2Rz

d[R] 2ktRz]-EIRJtRi]
=
+
RsIR'] - 2Ry[R]" =
0 &

dt

& [M'S
= GERJIR] - RsIR'S = 0

dA

Es ReTR][R] =
RIRY

dIRS-2RERS-2RIR
G
& =
= OcIR] =
I am
k4
d[R] = - ReTRc]-Re[R][Re] =
-

RotRe]-RIR] .
Go
[R2]
at k4
↑
177 10-3 .
1 473 10-3 mol
absabed = = , .

1 2
,
.
102