3. 1

moldm3s1moldm3min1 moldm3h1 da

3. 1. 1 2 H2O2 2 H2O + O2

t 2 [ H2O2 ] 2 [ O2 ] 2t 3[ H2O2 ] 3 [ O2 ] 3 t 1 [ H2O2 ] 1 [ O2 ] 1

O2 t1 t2 2 H2O2 2 H2O + O2 t 1 [ H2O2 ] 1 [ O2 ] 1t 2 [ H2O2 ] 2 [ O2 ] 2

t2 t3 2 H2O2 2 H2O + O2t 2 [ H2O2 ] 2 [ O2 ] 2t 3[ H2O2 ] 3 [ O2 ] 3

H2O2

H2O2 2 H2O2 2 H2O + O2

3. 1. 2

[ O2 ] t

AB

t1 t2 t0

t0 t0

t0 t0 t0 t0 +

t0 t0 +

0 AB O CD

AB CD

d[O2] [O2] dt t

H2O2 H2O2 2 H2O2 2 H2O + O2

1

2 t0

3 CE DE

CD t0

a A + b B g G + h H 0

3. 2

3. 2. 1

1 103 moldm3 2 HIg H2g+ I2g 973 K

s dm3 3.5 1028 = 5.8 104moldm3s1

1.

1. 4

E E E

NO2 + CO NO + CO2

NO2 + CO NO + CO2

a NO2 + CO NO + CO2

b NO2 + CO NO + CO2

P

P f

2.

Ea Ea Ea

2 SO2 + O2 2 SO3 Ea = 251 kJmol1 N2 + 3 H2 2 NH3 Ea = 175.5 kJmol1

HCl + NaOH NaCl + H2O Ea 20 kJmol1

1 NO2 + CO NO + CO2

NO2 + CO NO + CO2 N O C O

2. NO2 + CO NO + CO2

NO2 + CO NO + CO2 E E

NO2 + CO NO + CO2 E

Ea E E Ea

1

1 Ea rH1= Ea

2

2

1 + 2 NO2 + CO NO + CO2 rH = rH1+ rH2 = Ea Ea

rH = Ea Ea

Ea > Ea rH > 0 rH = Ea Ea

Ea> Ea rH < 0 rH = Ea Ea

rH Ea Ea T Ea

3. 3 3. 3.1

NO2 + CO NO + CO2

H2 + I2 2 HI 1 I2 2 I 2 I + I + H2 2 HI

H2 + I2 2 HI 12

3. 3. 2

aA + bB gG + hH i = ki [ A ]a [ B ]b

i = ki [ A ]a [ B ]b

H2O aA + bB gG + hH G G = kG [ A ]a [ B ]b

G = kG [ A ]a [ B ]b

aA + bB gG + hH A A = kA [ A ]a [ B ]b

A

[ A ][ B ] A = kA [ A ]a [ B ]b

i i AB [ A ][ B ] A = kA [ A ]a [ B ]b

ki ki ki A = kA [ A ]a [ B ]b

a b A = kA [ A ]a [ B ]b

a + b A a B b A = kA [ A ]a [ B ]b

aA + bB gG + hH a A b B a + ba + b

3. 1

1 i = ki [ SO2Cl2 ] SO2Cl2 SO2 + Cl2 1

2 i = ki [ NO2 ]2 2 NO2 2 NO + O2 2

3 i = ki [ NO2 ] [ CO ] NO2 + CO NO + CO2 3 2 2

3. 3. 3

3. 2 a A + b B g G + h H 1 1.0 1.0 1.2 102 2 2.0 1.0 2.3 102 3 1.0 2.0 4.8 102

1 2 [ A ]0 2 G0 2 G [ A ] 1 a A + b B g G + h H 1 1.0 1.0 1.2 102 2 2.0 1.0 2.3 102

1 3 [ B ]0 2 G0 4 G [ B ] 21 1.0 1.0 1.2 1023 1.0 2.0 4.8 102 a A + b B g G + h H

G = kG [ A ] [ B ] 2 1 G [ A ] 1 G [ B ] 2

1 G = kG [ A ] [ B ]2 1 kG

= 1.2 102dm6 mol2s1 G = kG [ A ] [ B ] 2

[ A ][ B ] G AB H

3. 3 H2 + I2 2 HI 1 I2 2 I 2 2 I I2 3 2 I + H2 2 HI

12 3 1 I2 2 I 2 2 I I2 3 2 I + H2 2 HI 123

1 I2 2 I 2 2 I I2 3 2 I + H2 2 HI

ABC D E 5 E ABC E 20 D 10

D 10

3 1 I2 2 I 2 2 I I2 3 2 I + H2 2 HI 3 i = ki3 [ H2 ] [ I ]2

i = k i3 [ H2 ] [ I ]2 H2 + I2 2 HI

k+ [ I2 ] = k [ I ]2 + =

i = ki3 [ H2 ] [ I ]2

i = ki [ H2 ] [ I2 ]

H2 + I2 2 HI H2 + I2 2 HI

3. 3 3. 3

3. 4 CH3CHO CH4 + CO

CH3CHO CH4 + CO

CH4

CH3CO CH3

[ CH3CO ] 2 = 3

[ CH3 ] 2 + 2 4 = 1 + 3

2 + 2 4 = 1 + 3

k1 [ CH3CHO ] = 2 k4 [ CH3 ]2

k1 [ CH3CHO ] = 2 k4 [ CH3 ]2

2 CH3 C2H6

Na + 2 H2O 2 NaOH + H2 i = ki 0

CO + Cl2 COCl2

i = ki [ A ]m [ B ]n H2 + Br2 2 HBr

HBr H2 + Br2 2 HBr

0 3 1 2

4 4

3. 3. 4 1. i = ki [ A ]m [ B ]n ki [ A ][ B ] 1 i = ki ki

i = ki [ A ]m [ B ]n ki ki ki

2. i [ A ][ B ]

i ki i = ki [ A ]m [ B ]n [ A ][ B ]

ki

3.

i = ki ki i moldm3s1

ki s1 i = ki [ A ]

i = ki [ A ]2

dm3mol1s1

n ki moldm3n1s1 dm 3 n1 mol n1s1

3. 4 aA bB

3. 4. 1

[A] = [A]0 ktd [A] = k d t

[A] = [A]0 kt

[A] = [A]0 kt

[A] = [A]0 kt [A]0 k t [A]

[A] t t1/2 [A] = [A]0 kt

[A] = [A]0 kt

k [A]0

3. 4. 2 A = k [A]

A = k [A]

ln[A] ln[A]0 = kt

ln[A] ln[A]0 = kt

[A] t

k

3. 5 14C 14C 9.60 1014 %

14C 1.10 1013 % 14C 5720

[A] t

k

1121 t = 1121 a

1

1

3. 5

400 K

Vant Hoff 10 K 2 ~ 4

Vant Hoff 1901 2 N2O5 4 NO2 + O2

3. 5. 1 k Arrhenius k T

k Ea R T A k

1 3

Ea A T k

1903

3. 6 C2H5Cl C2H4 + HCl A = 1.6 1014 s1 Ea = 246.9 kJmol1 700 K k

A = 1.6 1014 s1 Ea = 246.9 kJmol1

= 6.02 105 s1 A = 1.6 1014 s1 Ea = 246.9 kJmol1

710 K k710 = 1.09 104 s1 k700 = 6.02 105 s1 10 K 1.8

500 K 510 K k 3.2 700 K 710 Kk 1.8

Ea 500 ~ 510 K 700 ~ 710 K

T1 k1T2 k2 Ea A

21

3. 7 2 NOCl 2 NO + Cl2 T1 = 300 K k1 = 2.8 105 dm3mol1s1 Ea A T2 = 400 K k2 = 7.0 101 dm3mol1s1

= 101 kJmol1

EaT1k1 A = 1.07 1013 dm3mol1s1 Ea = 101 kJmol1 T1 = 300 K k1 = 2.8 105 dm3mol1s1

3. 5. 2

Ea A 3. 7 k T Ea A

Ea Ea

3. 6 3. 6. 1

Fe N2 + 3 H2 2 NH3

2 SO2 + O2 2 SO3 aV2O5 bNO2c Pt CO + 2 H2 CH3OH CuOZnOCr2O3

O2 O2

NH3 Fe Al2O3 Fe

Fe K2O Fe

3. 6. 2 1. NO2 2 SO2 + O2 2 SO3

2 MnO4 + 6 H+ + 5 H2C2O4 10 CO2 + 8 H2O + 2 Mn2+ Mn2+

t0 tA tA tB

tB

Fe Ag H2O2

2. 2 SO2 + O2 2 SO3 a V2O5b NO2c Pt

a b + c d

2 KClO3 2 KCl + 3 O2 MnO2 4 KClO3 3 KClO4 + KCl

CO + 2 H2 CH3OH CuO ZnO Cr2O3 CO + 3 H2 CH4 + H2O Ni Al2O3

3. A + B AB Ea

Cat.

rH

NO2 SO2 NO2

Fe N2 H2 N2 + 3 H2 2 NH3 Ea

N2 + 2 Fe 2 NFe NFe + HFe Fe2NH Fe3NH2 + HFe Fe4NH3 Fe2NH + HFe Fe3NH2 Fe4NH3 4 Fe + NH3 Fe H2 + 2 Fe 2 HFe

N2 + 3 H2 2 NH3

3. 7

12

3. 7. 1

1

K

K K

g + h =a + b K 1

Kp Kc

Kc Kp Kc Kp

c moldm3 p Pa R = 8.314 103 Padm3mol1K1

Kc Kp

H2O

K2 =K12 2 K 2 n K n

7 = 5+6 K7 = K5K6

3. 7. 2

[ A ] = 5 moldm3

pA = 10 100 kPa

1

x i = 1 x i = 1 1

K K K 1

K K p 1

100 kPa Kp K

= 100 kPa

= 1

3. 7. 3

3. 9 Kc = 9CO H2O 0.02 moldm3 CO

t0 0.02 0.02 0 0 t 0.02x 0.02x x x

= 9

[ CO ] 0.015 moldm3 x = 0.015 moldm3

= 75

Kc = 9 50 % Kc = 1

K

2 3 4 5 1

3. 7. 4

AB [ A ][ B ] Q

Q K

Q Kc Q < Kc

a A b B b B a A

= k [ B ]b = k [ B ]b b B a A

= k [ B ]b = k [ B ]b < 1

+ = k+ [ A ]a + = k+ [ A ]a + > + 2 a A b B

, = + < + + > + 2 < 1

Q > Kc Q = Kc = + Q < Kc

a K K b Q K Q K

3. 8. 1 a A + b B g G + h H Q

rGm < 0 rGm = 0 rGm > 0 rGm

rGm = 0 Q = K

rGm = RTlnK + RTlnQ

Q < K rGm < 0

Q > K rGm > 0 Q = K rGm = 0

3. 8. 2 H S G

rHm rSm rGm 298 K

3. 8. 3

Kc 3. 10 N2g+ 3 H2g 2 NH3g [ H2 ] = 0.15 moldm3 [ N2 ] = 2.1 moldm3 [ NH3 ] = 19 moldm3

Kc = 5.1 104 moldm32 N2g+ 3 H2g 2 NH3g

Kc = 5.1 104 moldm32

p K K ? c = 1 moldm3 K

p c N2g+ 3 H2g 2 NH3g

3. 11 2 NO2g N2O4g 298 K K

= 99.8 51.3 2 = 2.8kJmol12 NO2g N2O4g

K = 3.10 = 1.13

K

K = 8.9 1024

= 8.9 1024 100 kPa = 8.9 1019 Pa

298 K CaCO3 CO2 8.9 1019 Pa 298 K CO2 CaCO3

Na2SO410 H2Os Na2SO4s+ 10 H2Og 273 K K = 4.08 1025

Na2SO410 H2Os Na2SO4s+ 10 H2Og K = 4.08 1025

273 K Na2SO410 H2O H2O 0.364 kPa H2O Na2SO410 H2O

273 K H2O 0.611 kPa H2O 0.364 kPa

3. 9 3. 9. 1

AQ Q Q < K

Q Q K Q

K K Q K

3. 9. 2 [ CO ] = [ H2O ] = 0.005 moldm3 [ CO2 ] = [ H2 ] = 0.015 moldm3

H2Og [ H2O ] = 1.0 moldm3 CO

Kc = 9 [ CO ] = [ H2O ] = 0.005 moldm3 [ CO2 ] = [ H2 ] = 0.015 moldm3

Qc H2Og [ H2O ] = 1.0 moldm3

H2Og [ H2O ] = 1.0 moldm3 [ CO ] = [ H2O ] = 0.005 moldm3 [ CO2 ] = [ H2 ] = 0.015 moldm3

= 0.045

Qc < Kc t0 0.005 1.0 0.015 0.015 t 0.005 x 1 x 0.015 + x 0.015 + x Kc = 9 Qc = 0.045

x = 0.00495 = 9

[ CO ] 0.015 moldm3 = 75 %

[ CO ] = 0.02 moldm 3 = 99.75 %

3. 9. 3

N2g+ 3 H2g 2 NH3g 2

Qp pi = p xi xi p 2 pi 2

N2g+ 3 H2g 2 NH3g

Qp < Kp

Q K

3. 9. 4 K

T1 T2

21

RT1T2 > 0

T2 > T1 T2 T1 > 0

T2 < T1 T2 T1 < 0

Le Chatelier

K T rH

k T Ea 3. 7