Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

Solutions to odd-numbered problems

Topic 4
P4.3

496 nm, blue-green

Topic 5
P5.1

(a) 0.020

P5.3

a = / 21/5

P5.5

P5.7

xmax a

(b) 0.047

(c) 7 106

(d) 05

(e) 061

Topic 6

d2
e2

E
2
4 0 x
2me dx

P6.1

(a)

P6.3

(a) 1

d2
2
2m dx

(b)

d2
cx E
2
2m dx

(c)

(c) not an eigenfunction of i

(b) +1

Topic 7
P7.1

1
a
2

P7.3

P7.5

k2
2me

(a) (i) N 1a3

12

1
(ii) N 32
a05

12

P7.7

(a)

e 2
4 0 a0

(b)

2
2
d2
2

,
,
2me a0 2
2m
2m dx 2
2

Topic 8
P8.3

(a) (i) 0

(ii) i kx

Oxford University Press, 2014.

(b) (i)

xp x 2
2m

(ii)

i p x
2m

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

Topic 9
P9.1

1.24 1039 J , 2.2 109 , 1.8 1030 J

P9.3

(a)

P9.5

1

L

1
2

(b)

1 1

0.0908
4 2

(c)

4 x
L

1/ 2

Topic 10
1

P10.1

(e L e L ) 2

1 , 16 (1 )e2 L

16 (1 )

P10.3 (a)

T A3 2 A3 A3*

4k12 k22
(a 2 b 2 )sinh 2 (k2 L) b 2

where a 2 b 2 (k12 k22 )(k22 k32 ) and b 2 k22 (k1 k3 ) 2

P10.5

1.2 106

Topic 11
P11.1

8.86 1039 J , 1.111030 J

P11.3

1.6 106 m , 1.6 m

P11.5

6.9 1010 m , 0.69 nm

P11.7 (a) n / 2

P11.9

(b)

n2
6

h 2 n12 n2 2

E
8m L12 L2 2

Topic 12
1 2

P12.3

1 mkf
2 2

P12.5

3 (2v 2 2v 1) 4
4

Oxford University Press, 2014.

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P12.7 (b) 9V0

(c) the oscillations are not excited
(d) magnitude of the wavefunction
will not fall off so sharply with increasing displacement, so the energy levels will become
progressively closer.
P12.11 (a) e

/2

, e| |

/2

(c)

Topic 13
P13.1 (a) N = 1/2

(b) , 1/4, +,

P13.3

1.53 103 m , 1.53 mm

P13.5

, 0
1
21/ 2

P13.9 (a) no uncertainty in lz,

(c)

(b)

2mp r 2

(d)

1
2

Topic 14
P14.1

7.59 104 m = 0.759 mm

1/ 2

P14.3 (a) N = 1/(12)1/2

(e)

17 2
7
17
,
, 3.9 1023 J ,
4
6I
3

P14.7 0
P14.9

y z ,
i z
y i

z x ,
z i
x

x y , lz
x
i
y

Topic 15
P15.1 (a)

P15.3

a
L

a
sin

(b)

sin = 0.1984
10
10

0.08664m3 g 2 L4 32m2 gL3 [(1) n 1]n

,
2 h2 (n2 1)3
h2

Topic 17
P17.1

n2 6

Oxford University Press, 2014.

2mp r 2

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P17.3

aPs 2a0 , E1 Ps 12 E1 H

P17.5

K 60

Topic 18
P18.1

0420 pm

P18.3 (a) 106 pm

(b) r = 1.76 a0/Z

P18.5 (b) node 3 3 and node 3 3 , node 0 and node 4 , node 0

P18.7

r 266 a0

P18.9 (a)

Z
a0

(b)

Z
4a0

(c)

Z
4a0

Topic 19
P19.1

cos1

ml
, 5444 , 0
{l (l 1)}1 2

Topic 21
987663cm1 , 137175cm1 , 185187 cm1 , 122.5 eV

P21.1

P21.3

P21.5

3.3429 1027 kg , 1.000272

P21.7

l 1 and ml 0 or 1

Li2

P1 2 and 2 P3 2 , 2 D3 2 and 2 D5 2 , 2 D3 2

Topic 22
P22.1

Z 3/ 2 e / 2 2 sin

1/ 2 ( cos 31/ 2 sin ) , 120

(24 )1/ 2 a3/ 2 2

8

Topic 23
P23.1 1.87106 J mol1 = 1.87 MJ mol1

Oxford University Press, 2014.

(c) r 3s

27a0
2

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

EH1s

P23.3

j k j0
j k j0
, EH1s

1 S R
1 S R

P23.5 (b) 2.5a0 = 1.31010 m, 0.555j0/a0 = 15.1 eV, 0.565j0/a0 = 15.4 eV, 0.055j0/a0 = 1.5 eV,
0.065j0/a0 = 1.8 eV

Topic 24
P24.1 2.1a0
P24.3 /4 or 3/4

Topic 25
A B 2 S

P25.1

2(1 S 2 )

B S
1 S

A B

1
2(1 S 2 )

1/ 2

4( A S )( B S )
A S ( A S )( B S )

,
,
1 S 2
( A B )(1 S 2 )
( A B ) 2

( A S )( B S )
( A B )(1 S 2 )

P25.3 (i) E/eV = 10.7, 8.7, and 6.6

(ii) E/eV = 10.8, 8.9, and 6.9

Topic 26
P26.1 E = O,

1
12 2
O C ( O C ) 1
2
( O C )2

12 2
4 2
, ( O C ) 1
1
2

( O C )
( O C )2

4 2
O C

P26.3 (b) 2 , 0.988, aromatic

(c) 1.657 , 1.518, not aromatic

P26.7 PN = xPN1 PN2

P26.9 (a) and 2

(b) 413 kJ mol1

(c) 849 kJ mol1 ,

3( 2) 212kJ mol1 , 3 425kJ mol1

Topic 28
P28.1
(a)

Ethanol

Oxford University Press, 2014.

AM1*

PM3*

exp

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e
C1C2 / pm
C1O / pm
C1H / pm
C2H / pm
OH / pm
C 2C1O / o
C1OH / o
HC1H / o
HC2H / o

f H O g / kJ mol1

Dipole / D
*
Spartan 10TM

(b)

151.2
142.0
112.4
111.6
96.4
107.34
106.65
108.63
108.24
262.18
1.55

1,4-dichlorobenzene
C1C2 / pm
C2C3 / pm
C1Cl / pm
C2H / pm
ClC1C2 / o
C1C2H / o
ClC1C2H / o
f H O g / kJ mol1

dipole / D
*
Spartan 10TM

151.8
141.0
110.8
109.7
94.7
107.81
106.74
106.98
107.24
237.87
1.45

AM1*
139.9
139.3
169.9
110.1
119.71
120.40
0.00
33.36
0.00

153.0
142.5
110
109
97.1
107.8

235.10
1.69

PM3*
139.4
138.9
168.5
109.6
119.42
120.06
0.00
42.31
0.00

exp
138.8
138.8
173.9

24.6
0.0

Topic 29
P29.1

Features Calculated with Full CI, CCSD(T) and RIMP2 Methods

Bond length (R) in pm and energies in zJ

He2
Full CI *CCSD(T)/6-311++G(2df,2p) *RI-MP2/6-311++G(2df,2p)
R
297
321
301
E0 2EHe 0.039
0.00741
0.165

T. van Mourik and J.H. van Lenthe, J. Chem. Phys., 102(19), 7479 (15 May 1995).
*
Spartan 10TM

P29.3 0 0 0 0

P29.5

n 0 H 1 0 0 d

n
0
0
E0 En
n 0

H 22 2 b 1 h1 b 1 d1 12 AA AA 4 AA AB AA BB 2 AB AB ,

H 00 2EH 12 AA AA 4 AA AB AA BB 2 AB AB , H 02

Oxford University Press, 2014.

1
2

AA AA AA BB H

20

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

Topic 30
P30.1

VXC r 53 C r

2/3

Topic 31
P31.1 (a) D3d

(b) D3d , C2v

(c) D2h

(d) D3

(b) A1 + 3E

(c) A1 T1 T2

(e) D4d

P31.3 S4 , C2, S4

Topic 32
P32.1

trans-CHCl=CHCl

P32.3 A1 + B1 + 2B2
P32.7

+1 or 1, 1 , 1

P32.9 (a) 2A1 A2 2B1 2B2

P32.11 (a) E 2C3 3C2 h 2S3 3 v , D3h

(d) A2u T1u T2u

(d) A1 E

Topic 33
P33.1

A1 T2 , s and p, (d xy ,d yz ,d zx )

P33.7

4A1 +2B1 +3B2 +A2

P33.9 (a) 7A 2 7B1 ,

1
2

(a a)

1
2

(b b) 12 (g g ) , 12 (a a) 12 (b b) 12 (g g)

Topic 34
P34.1

0.7 D , 0.4 D , 0

P34.5

0.123

P34.7

3.68 1039 J 1 C2 m2 , 3.311029 m3 , 1.32 D

Topic 35

Oxford University Press, 2014.

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P35.1

4.3 1028 J 2.6 104 J mol1

P35.3

6C
r7

P35.5

2 N A C6
3 M d 3
2

Topic 36
P36.1

b
, 1.11
Vmo

(b) 0.15 dm3 mol1

P36.3 (a) 87 cm3

P36.7 13.6 dm3 mol1, attractive, 2%

Topic 37
1

P37.1

3.61105 g mol

P37.3

V 3 3 / 2 a2c

P37.5

834 pm , 606 pm , 870 pm

P37.7 4
2

P37.9

1 h k l

d2 a b c

P37.11 simple (primitive) cubic lattice, a = 344 pm

P37.13 628pm , gave support
P37.15 0
P37.17 (a) 14.0o , 24.2o , 0.72o , 1.23o

Topic 38
P38.1

0340

P38.3

7.654 g cm3

Oxford University Press, 2014.

(b) RCCl = 176 pm and RClCl = 289 pm

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P38.7

146 kJ mol1

P38.9

6.694

Topic 39
P39.7

8.81109 m3 mol1

Topic 40
P40.3

4.4 103

P40.5

A J 0 1 e L / , A = '[J]0

P40.9

1
4
3
1
2

max v1/ 2 , 5.7 10 dm mol cm

2 ln 2

1/ 2

P40.11 498 kg mol1 , 51.3 nm

P40.13 (a) receding , 1.128 103 c = 3.381105 m s1
P40.15 2 kT / mc 2

1/ 2

Topic 41
P41.1

meff R 2

Topic 42
P42.1 596GHZ, 19.9 cm1, 0.503 mm, 9.941 cm1
P42.3

128393pm , 12813pm

P42.5

116.28 pm , 155.97 pm

P42.7

14.35 m1 , 26 , 15

P42.9

1
1
kT
kT

, 30 ,
, 6
2
2
2hcB
hcB

12

12

Topic 43

Oxford University Press, 2014.

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P43.1

14281cm1 , 3.36 eV , 938 N m1

P43.5

2De 12

P43.7

112.83 pm , 123.52 pm

P43.9

B 0 = 10.433 cm-1, B1 = 10.126 cm-1

x2

P43.11

1
(v ) . Rotational constant B decreases, B decreases with increased anharmonicity
kf

P43.13 (b) 12.8195kJ mol1

(c) 1.85563 103 N m1

(d) 1.91cm1

(e) 113 pm

Topic 44
P44.3 (a) C3v (b) nine (c) 3A1 3E

(d) all modes are infrared active

(e)

all modes may be Raman active

Topic 45
P45.1 1g21u21u42g01g1
P45.3

49364 cm1

Topic 47
P47.1 (a)
Nuclide
2

Spin I

Sensitivity ratio (

0.85745

0.409

0.00965

1
2

0.7023

0.251

0.01590

0.40356

0.193

0.00101

19

1
2

2.62835

0.941

0.83350

31

1
2

1.1317

0.405

0.06654

1
2

2.79285

13

14

Topic 48
P48.1

Sensitivity ratio( v )

29 Tm-1

Oxford University Press, 2014.

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P48.3

Both fit the data equally well

P48.5 cos = B/4C

Topic 49
P49.1

400 106 Hz 8Hz , 029s

P49.3 (a)

2
T2

(b)

2(ln 2)
T2

P49.7 0.58 mT

Topic 50
P50.1

2.8 1013 Hz

P50.3

6.9 mT , 2.1mT

Topic 51
P51.1 (b) {2, 2, 0, 1, 0, 0} and {2, 1, 2, 0, 0, 0}
P51.7

e Mgh RT , 0.363 , 0.57

Topic 52
P52.3 (a) (i) 5.00
P52.5

(ii) 626

(b) 100 , 0.80, 6.58 1011 , 0122

1.209 , 3.004

P52.7 (a) 1.049

(b) 1.548 , 0.953 , 0.645 , 0.044 , 0.230 , 0.002 , 0.083

P52.9 (a) 660.6

(b) 4.26 104

Topic 53
P53.3 (a) 104 K

(b) 1 a

Topic 54

Oxford University Press, 2014.

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P54.1

pV NkT nRT

Topic 55
P55.1

V nb 2 1 1
nRT ln 2
n a
V1 nb
V2 V1

(a) 17 kJ

Topic 56
P56.1

62.2 kJ mol1

P56.3 w = 0, U 2.35 kJ , 3.03 kJ

P56.5 increase
P56.7 (a) 29.9 K MPa 1

(b) 2.99 K

Topic 57
P57.1

1270 kJ mol1

P57.3

67.44 , n 0.9253 , 6625.5 kJ mol-1 , 2.17 per cent

P57.5

994.30 kJ mol1

P57.7

802.31 kJ mol1

P57.9

37 K , 4.09 kg

Topic 58
P58.1

16 m , 080 m , 28m

P58.3 0.385, 0.0786, 0.0206

P58.9

N 2
kT 2

Oxford University Press, 2014.

(b) 18kJ , 1.5 kJ

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P58.11 CV ,m R 1

2
3

1 R
16 R

... ,

45 T 945 T

1
C
R
V ,m
xq R

12e2/ x (115e4/ x 20e6/ x 84e 10/ x 175e 12/ x 105e 16/ x ...) ,

1
C
R
V ,m
xq R

12e2/ x (115e4/ x 20e6/ x 84e 10/ x 175e 12/ x 105e 16/ x ...)

eE /T
E

3R E /T
2
1)
T (e

P58.13 CV ,m

(b), (c) ( K ( K 4))1 2 , 2 CV ,m (H) (1 )CV ,m (H2 ) ,

P58.15 (a) 87.55K , 6330 K

K eqi

kTi H2i

e ( D RTi )

p O qVi qRi Hi

V e (V 2Ti )

R
V Ti
Ti 1 e

, 1.5R , 2.5R

P58.17 (a) q 19.899, q 19.558, and q 576.536

R

qR 3.007, qR 2.979, and qR 118.5

P58.23 nR
T
V nb
p
na
(V nb) ,

(V nb)
2
nR
nR
RV
p V

P58.25 T =

p
P58.27 c

1 2

, 322 m s-1

Topic 60
P60.3

1994 J mol1 K 1

P60.7

1 2
2

2 e2 m m
m h

R ln 2
, R ln V

m 2 me
h NA

Topic 61
P61.5 1.00 kJ

Topic 62

Oxford University Press, 2014.

(b)

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e
P62.1 (a) 21.3J K-1 mol-1 , 21.7 J K-1 mol-1 , 04 J K 1 mol1

(b) 109.7 J K-1 mol-1 ,

111.2 J K-1 mol-1 , 1.5J K 1 mol1

P62.3 (a) 43.9 kJ , 43.9 kJ , 118.1J K 1 , 145.9 J K 1 , 28 J K 1

(b) 49.9 C 3231K , 38.4 kJ ,

119.8J K 1 , 129.2 J K 1 , 9 J K 1

P62.5

45.4 J K1 , 51.2 J K1

P62.7

dS
CA ln(Ti TS )
dt

Topic 63
P63.1 (a) 200.7 J K1 mol1

(b) 232.0 J K1 mol1

P63.3

41.16 kJ mol1 , 42.08 J K1 mol1 , 40.84 kJ mol1 , 41.08 J K-1 mol-1

P63.5

34.4 kJ mol-1 , 243 J K 1 mol1

Topic 64
P64.1 (a) 50.7 J K 1 , 11.5J K 1
indeterminate

(c) 3.46 103 J ,

(d) 39.2 J K 1 , 39.2 J K 1

P64.3 (a) 35 J K1 mol1

(b) 12 W m3 , 1.5 104 W m3 , 0.46

Topic 65
P65.1

(b) +3.46 kJ , indeterminate

513.5kJ mol1

Topic 66
P66.1

501kJ mol1

P66.3

21kJ mol1

Oxford University Press, 2014.

mol ATP
mol glutamine

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P66.5
P66.7

VS

T , S
p S V

T V

C p dT TV dp , TV p , 0.50 kJ

Topic 67
P67.1 (i) molten globule form is not stable

Topic 68
P68.1 (a) yM = 0.36

(b) yM = 0.81

Topic 69
P69.1

1960 K , 111Torr

P69.3

234.4 K

P69.7

T T

P69.9

C p d ln T

1
T

P69.11 C p ,m

Topic 70
P70.1

1558kPa , 4703kPa

Topic 71
1

P71.1

125 105 g mol , 1.23 104 dm3 mol1

P71.3

R(Tb *) 2
xB
vap H

Topic 72

Oxford University Press, 2014.

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e
(b) 75.63 cm3 mol1 ,

P72.3 (a) V1 Vm,1 a0 x22 a1 (3x1 x2 ) x22 , V2 Vm,2 a0 x12 a1 ( x1 3x2 ) x12
99.06 cm3 mol1

P72.7 GE is reasonably consistent with the model regular solution

P72.9 72.53 cm3 mol1

Topic 73
P73.1 (a) +4.48 kJ mol1

(b) 0.102 bar

P73.3

0.02054

P73.5

0007 mol H2 , 0.107 mol I2 , 0786 mol HI

P73.7

1.2 108 , 2.7 103

P73.11 (a) KH(Mb) = 2.0, KH(Hb) = 36.0

Oxygen partial pressure
p / kPa
p / Torr
1.0
7.5
1.5
11.3
2.5
18.8
4.0
30.0
8.0
60.0

s
Mb
0.79
0.85
0.90
0.94
0.97

Hb
0.01
0.04
0.14
0.38
0.81

(b)
p / kPa p / Torr s(Hb)
1.0
7.5
0.002
1.5
11.3
0.01
2.5
18.8
0.07
4.0
30.0
0.33
8.0
60.0
0.89

Topic 74
P74.1
T/
K
K

300 400 500 600 700 800 900 1000

945 273 132

Oxford University Press, 2014.

83

61

49

42

37

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

Topic 75
P75.1 (a) 9.24 , 31.08 (b) 12.9 kJ mol1

(c) 161 kJ mol1

(d) 248 J K 1 mol1

P75.3

3 R B CT , 70.5 J K 1 mol
2

P75.5

78 0.161 T K

P75.7

156 kJ mol1

P75.9

r G T r G T (T T )r S T T , T a T , T b T , T c , 22531 kJ mol1

Topic 76
P76.1 (a) 1.23 V

(b) 1.11 V

Topic 77
P77.1a (a) 4.0 103 , 1.2 102 (b) 0.74 , 0.60 (c) 5.9 (d) 1.102 V

(e) +1.079 V

P77.3 (a) E O (38.54 mV) ln(41/3 b) (38.54 mV)ln( ) (b) 1.0304 V

(c) 236.81 kJ mol1 ,

198.84 kJ mol1 , 6.84 1034

(d) 0.763

(e) 0.75

P77.5

74.9 kJ mol1 , 80.0 kJ mol1 , 17.1 J K 1 mol1

P77.7

131.25 kJ mol1 , 167.10 kJ mol1 , 56.7 J K1 mol1

P77.11 (b) +0.206 V

Topic 78
1/ 2

P78.3

2kT
18.9 s , v(most probable) vmp

m
1/ 2

P78.7

2
kT
m
f (v) ve mv 2 kT ,

kT
2m

P78.9 (a) 39%

(b) 61%

Oxford University Press, 2014.

1/ 2

2 RT

M
1/ 2

RT
or

2M

(c) 0.533 , 53% , 47%

(f) 87.2 J K1 mol1 , 262.4 kJ mol1

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

2 n 1 2kT
P78.11 1/ 2
!

2 m

n/ 2

n 1!! 2kT n / 2
2n / 2

P78.13 (a) 11.2 km s1 , 1.19 104 K , 2.37 104 K , 1.89 105 K

4.80 103 K , 3.84 104 K

(b) 5.04 km s1 , 2.42 103 K ,

P78.15 0.25 J cm3

Topic 79
P79.1 (a) = 0.602 nm2 , d = (/)1/2 = 438 pm
P79.3

(b) = 0.421 nm2 , d = (/)1/2 = 366 pm

2.37 1017 m2 s1 , 2.85 J K1 m1 s1

Topic 80
P80.1

10.2 kJ mol1

P80.3

12.78 mS m2 mol1 , 2.57 mS m2 (mol dm1 )3/ 2

P80.5

12.6 mS m2 mol1 , 6.66 mS m2 (mol dm1 )3/ 2

(a) 12.02 mS m2 mol1

(b) 120 mS m1 (c)

172

P80.7

0.83 nm

P80.9

93 kJ mol1

Topic 81
P81.1 (a) 12 kN mol1 or 2.0 1020 N molecule1 (b) 16.5 kN mol1 or 2.7 1020 N molecule1 ,
24.8 kN mol1 , 4.11020 N molecule1
P81.7

RT
r
2 Dt

where

r xi yj zk

P81.9 N > 60
2

P81.11 1.7 10 s
P81.13 Dt N 2 / 6

Topic 82

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Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P82.1 second order

Topic 83
P83.3 second-order, kr 00594 dm3 mol1 min 1 , 2.94 g
P83.5 7.0105 s1, 7.3105 dm3 mol1 s1
P83.7

6 1014 mol dm3 s1 , 4.4 108 s 14 yr

P83.9 first-order, 5.84103 s1, kr = 2.92103 s1, first-order, 1.98 min

P83.11 3.65103 min1, 190 min
P83.13 2.37 107 dm3 mol1 s1 , kr = 1.18107 dm3 mol1 s1, 4.98 103 s
P83.15 first-order, third-order

(2 x A0 ) B0
1
ln

3 A0 2 B0 A0 (3x B0 )

P83.17

P83.19

2n 1 1

34

n 1

Topic 84
P84.3

kr kr e ( kr kr )t
kr{[A]0 [B]0 } kr {[A]0 [B]0 }
,

{[A]0 [B]0 } ,

kr kr
kr kr
kr kr

P84.5 (a) 8ka ka[A]tot (ka )2

(c) 1.7 107 s1 , 2.7 109 dm3 mol1 s1 , 1.6 102

Topic 85
P85.3 1.67104 J mol1, 16.7 kJ mol1, 1.14 1010 dm3 mol1 s1
P85.5 13.7 kJ mol1, 8.7108 dm3 mol1 s1

Topic 86
P86.1 steady-state approximation
P86.3 steady-state intermediate

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Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P86.5

kr K1 K2 [HCl]3 [CH3CH=CH2 ]

Topic 87
(b) 015

P87.1 (a) 4.35 1020 m2

P87.3

1.7 1011 mol1 dm3 s1 , 3.6 ns

P87.5

3.12 1014 dm3 mol1 s1 , 193 kJ mol1 , 7.29 1011 dm3 mol1 s1 , 175 kJ mol1

Topic 88
(b) 4 1010 m = 0.4 nm

P88.3 (a) 6.23 106 m3 mol1 s1 = 6.23 109 dm3 mol1s1

Topic 89
P89.1 Ea = 86.0 kJ mol1, +83.9 kJ mol1, 19.6 J K 1 mol1 , +79.0 kJ mol1
P89.5 two univalent ions of the same sign
P89.7

log Ka log

1 2
[HA]
2 AI 1 2 , v102 AI

[A ]

P89.9 (a) 1.37 106 dm3 mol1 s1

P89.11

v3 E0 / RT
e
(v ) 2

(b) 1.16 106 dm3 mol1 s1

(a) 2.7 1015 m2 s1

(b) 1.11014 m2 s1

Topic 90
P90.1

I I 0 e N L

Topic 91
P91.1
p/Torr

84.1

11.0

2.89

0.569

0.120

0.067

1/(p/Torr)

0.012

0.091

0.346

1.76

8.33

14.9

104 kr / s1

2.98

2.23

1.54

0.857

0.392

0.303

Oxford University Press, 2014.

Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e
104 / (kr / s1)

0.336

0.448

0.629

1.17

2.55

3.30

Topic 92
P92.1

vmax
1
1
K S0

Rate law based on rapid pre-equilibrium approximation , ka kb

P92.5 2.31 mol dm3 s1, 115 s1, 115 s1, 1.11 mol dm3, 104 dm3 mol1 s1
P92.7 (b) pH 7.0

Topic 93
P93.1

1.11

P93.3 (a) 6.9 ns , 0.101 ns1

P93.5

1.98 109 dm3 mol1 s1

P93.7 3.5 nm

Topic 94
P94.1 (e) kr (kAAkDDK)1/2
P94.3

1.15 eV

Topic 95
P95.1

76.9 kJ mol1 , 348.1 kJ mol1 , corner is the likely settling point

P95.3 (a) 1.61 1015 cm2

P95.5

(b) 1.14 1015 cm2

R Req 1 e kr t where kr kn a , R Req e kr t where kr koff

Topic 96
P96.3 (a) 165, 13.1 cm3
P96.5

(c) 1.86 1015 cm2

(b) 263, 12.5 cm3

5.78 mol kg 1 , 7.02 Pa 1

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Atkins, de Paula & Friedman: Physical Chemistry: Quanta, Matter, and Change 2e

P96.7

20.0 kJ mol1 , 63.5 kJ mol1

P96.9 (a) R values in the range 0.975 to 0.991

b H 157 kJ mol

(b) 3.68 103 , 8.67 kJ mol 1 , 2.62 105 ppm1 ,

Topic 97
P97.1

p p0 p0
kr pNH 3
p
, kc
, kc = 2.510 kPa s1

ln
t
t
p0
K pH 2

Oxford University Press, 2014.