r r

r


r r

r







r




r

r r r r

r
r
r r


s

r

t

P
t

t P

t
q
q r tt s


t


q
t
q
r

P

t t
P P t t

P P t t

viii

s



s

11

P





P

P
-

P
t



P
P
q
r s q
q

PP

P P




P


r rr


q s
q t
P
P s,p,d,f
q
r
q P q
q
q
P
q

xii

K,

I-IV

SOME BASIC CONCEPTS OF CHEMISTRY

SI

q rs

r

(AZT)











(stratosphere)
(Ozone depletion)
(CFC)

qrst r t s rrs rr







(i)
(ii)

(iii)

P







q q


r

s
t

s

s
t





s

t
s

s

s

t

r

P


t s
t

(H 2O)

(CO 2 )

t


P
P



P


P

(pop)






qrs
P P
P

P P
P


P



P P

P P

P 6 m

m P P
P


(the English System)
(the Metric System)

P
P

P P

(SI)
P Le System International d'Units), S.I. P

P (conference Generale des Poios et
Measures, CGPM) CGPM


P
SI



SI
P
SI P
P



P

P
P

r r
SI

l
m
t
I
T
n
Iv

SI

m
kg
s
A
K
mol
cd

r SI

qs

qt

q qs

q qs

133 P

qs

P

P
2 107

q q qs

t qs qs

(elementary entities) kg
P
(mol)

(specify) P P

tt qs

540 1012

t t

t




P NMI
t
t
t
NPL

t
t


t
r

1024
1021
10

18

10

15

1012
109
106
103
102
10

10
102
10

10

10

1012
10

15

10

18

10

21

1024

SI

r r qs

y
z
a
f
p
n

m
c
d
da
h
k
M
G
T
P
E
Z
Y

SI

1 = 1000

SI
m3

cm3 dm3

(L)
SI
1L = 1000 mL 1000 cm3 = l dm3

SI

SI =

kg m3

g cm3 (g)

cm3

r
C
F K
K SI

0 100

P 32F 212

qst
0C

(Pt-Ir)


Pt-Ir











Pt - Ir P

P

0C (273.15 K) Pt-Ir


(Laser)
1.65076373106

CGPM

qrs
t t t
t
t 2g



t
g
t t
t t
t t
t t
t t
t
t t
t t
t
t

t t
N 10n
n t
t N t
N
t
232.508 2.32508
2
10
t t
t
t 1.6 104 t
t t
t t (4)
t
t
t t

t

r




P

r r q s
t t r q
r 6.65 104 8.95 103
r
tr
6.65 104

0.895 104

s t t r
(6.65

0.895) 104 = 7.545 104

t r
2.5 102 4.8 103
= (2.5 102) (0.48 102)
= (2.5 0.48) 10-2 = 2.02 102

rr
r r
q ts sr r rs r
tr q

r r q r
r
r r q
2.00 g r
1.95 g 1.93 g r r q
sr r
q
1.94 g 2.05 g r r q
r q r
2.01 g 1.99 g r
r q q r
1.4 t r q

/g

r (g)

1.95
1.94
2.01

1.93
2.05
1.99

1.940
1.995
2.000

r rr
r tr q
r t r r q rr
r r tr
rr r tr
r 11.2 mL
r r 11 r 2 r
r r 1 rr q
sr r r 1
rr r tr q
r q t
t
(1) r q
285 cm r 0.25 mL
q
(2)
rq r
srr q r
q
(3) r r q
r q
(4) r
r r r
r q
r r
rq
q
r r
q r r
r r q
2
2
1 10 , 1.0 10
2
r 1.00 10 r q
(5) r r
r

s r r t r

10

t
2 = 2.000000 20 = 20.000000

4.01 102 8.256 103


t
t
t
12.11
18.0
1.012
31.122

18.0




t
t

P

t

(rounding off)

t 5

t t

t

t t

t

t
r
t t
t


t
t

qsq


(factor label method),
(unit factor method)
(dimensional analysis) t

3 (inch) cm

t 1 inch = 2.54 cm

t t
t

P t

t tP
t


t
t
t

t 2L m3
t

t 1L = 1000 cm3

11

m3

(s)

(day) = 24 (h)

q rs t

r



t

2g
2g

16 g

32 g

18 g

34 g

16 g 32 g

(2g)
16:32 1:2

12

P



100 mL 50 mL
100 mL t
+

100 mL

50 mL

100 mL

100 mL 50 mL
2:1
qr
s

q


1811
q s
q
q s



s

q
s q
s q q
q
q

q
q q

Journal de Physidue

50 tr 1860
t




q
(atomos)


(460-370 BC)

P
(A New System of Chemical Philosophy)
s

13

amu


=

= 1.0078 u
= 1.0080 u

s 16(16O)
15.995 amu
amu u s
(unified mass)
s

q r s t

t

r


12 (atomic mass
unit-amu)
r

1 amu = 1.66056 1024g

= 1.6736 1024g

s t

r s


r

(%)

(u)

98.892

12

1.108

13.00335

2 10

10

14.00317

s s

= (0.98892) (12 u) + (0.01108) (13.00335 u)

+ (2

1010) (14.003.17 u) = 12.011 u

s





s

14

= (12.011u) + 4 (1.008 u) = 16.043 u

=
2 + 1

= 2 (1.008 u) + 16 u = 18.02 u

=
6 (12.011u) + 12 (1.008 u) + 6 (16.00 u)
= (72.066 u) + 12.096 u) + (96.00 u)
= 180.162 u

Na+ Cl

1.10

NaCl



=
+
= 23.0 u + 35.5 u = 58.5 u

qrst t





Score, 144
(gross)



SI mol




12 12g 0.012
kg


12

1.992648 1023g
12 g







6 022 136 700 00 00 00 00 00 00 00

= 6.022 1023
= 6.022 1023
=
6.022 1023
1.11

15

= 18.02 g

P


qrs t r
r r r



= 18.02 g mol-1
= 58.5 g mol-1

ts qrs qr tq qq t
t t r r

16

4.07% 24.27% q
71.65% 98.96
g s

r 100 g
s
100 g 4.07 g 24.27 g q
71.65 g


r s

q s

s

t
2.021 q r 2.021
t







PP


(stricheion),
(metron),

H : C : Cl s 2 : 1 : 1


s




r



s

s






n

n = 2
r
q r
s
s



s
s
s



q




g
(s) (l)

17

P
s s
s s

q

r
t
r

q
r
r

q q q
C C


H r H H
H
q q q
O

q q q
r



(subscript) r

18

qr
qr

16 g (g)

(i)
(ii)
2
2
1

P P

qr
qr

qr q qr
qr

q (limiting reagent)

t
0.5
0.5


50.00 kg N2(g) 10.00 kg H2(g) NH3(g)

NH3(g)

NH3 qr

qr


N2(g)

qr
H2(g)
17.86 102 H2(g)
= 17.86 10 2

19

= 5.36 10 H2(g)

4.96 103 H2(g)

H2(g)
NH3(g) H2(g)

3
3.30 10 NH3(g)
(g)
NH3 (g) = 17.0 g NH3 (g)
3

4.96 10 )
H2(g) 2 NH3(g)
4.96 103

3.30 10

P


P (w/w%)





s qrt

qrt

A 2g 18g
(A) P

A P =

1L

A B

nA nB

ts
ts
s
t

NaOH 1M 0.2 M

1 M NaOH 1L 1
NaOH 0.2 M IL
NaOH
M1 V1= M2 V2
M V M1=0.2;
(M) =

20

V1=1000 mL r M2=1.0;

V2 r r
.2 M 1000 mL = 1.0 M V2

1 L 0.2 NaOH
r 0.2 NaOH
r 1L
(1M) NaOH r r
0.2 NaOH r
r r
1 L 1000 mL r 1 r
r 0.2 r

r 1 M NaOH 200 mL r
r r r 1L
200 mL (NaOH)
0.2 r (1000 mL)
r r (0.2)
rr NaOH

1 kg P
m
r r
qst qt s
t t
r r
qs t

NaOH r

4 g NaOH r
r r
250 mL r

r r
r r r r

1

3 M NaCl l.25 g ml

r
m = 3 mol L

1 L NaCl = 3

58.5

= 175.5 g
1 L

= 1000 1.25gm

= 1000 1.25 = 1250 g

= 1250 gm

= 1.25 g mL1

= 1250 175.5
= 1074.5 g

qst qt s
t t

t qs

r r
r r
r r
(Stock solution) r
r r
rr r r
r r

21

r PP P


t


SI

1031 1023
P r PP P
qs PP


sP PP
P s P Pr P s Pr Pr P s
P qs PsrP P s
PPPP P s P P PP P r
t PP sP 12C u


PPsPP
P P

PP PP PP (6.022 1023)


rr PPs
t
t PsPqq t

22

(i) H2O

(iii) CH4

(Na2SO4)
69.9%
30.1%

(i)
(ii) 16 g
(CH3COONa) 500 mL, 0.375
82.0245 g mol1

69% 1.41 g mL1
100 g (CuSO4)

g g

%
P

Cl

75.77

34.9 689

Cl

24.23

36.9659

35
37

(ii) CO2

(ii)
(iii)
20g (C12 H22 O11) 2L

0.793 kg L1 0.25 M 2.5 L

SI

(C2H6)

(i)

1 Pa = 1 Nm2

1034 g cm2
SI


q
(i)
106
(ii)
109
(iii)
106
(iv)
1015
(v)
10

15 ppm
(i)

(ii) t t

(i)

0.0048

(iv)

500.0 (v) 6.0012

(ii) 234,000

(iii) 8008

t
(i)

0.0025

(ii) 208 (iii) 5005

(v)

500.00

(vi) 2.0034

(iv) 126,000

t t
(i)

23

34.216

(ii) 10.4107

(iii) 0.04597

(iv) 2808

t t


t
(i)

14 g

16 g

(ii)
(iii)
(iv)

14 g
28 g
28 g

32 g
32 g
80 g

P

(i)

1 km

...........

mm

............ pm

(ii) 1 mg
(iii) 1 mL

=
=

...........
...........

kg
L

=
=

............ ng
............ dm3

t t
t
(i)
A 300 P + B 200 P
(ii) A + 3 B
(iii) A 100 P + B 100 P
(iv) A 5 + B 2.5
(v)
A 2.5 + B 5
t P t

3.00 108 m s 1

2.00 ns

t t

(i)

2.00 103 g
1.00 103 g t
t

(ii)

(iii)

24

0.50 M Na2CO3

r
r r
0.5 mol Na2CO3

(i)

28.7 pm

(ii) 15.15 pm

(iii) 25365 mg

r
(i)

1 g Au (s)

(ii) 1 g Na (s)
(iii) 1 g Li (s)
(iv) 1 g Cl2 (g)

r r r r r r
r r
12C (g)
r r

(i)

(ii) P

0.040

(iii) 0.0125 + 0.7864 + 0.0215

r r r r r

q
36

Ar

35.96755 mol1

0.337%

Ar
40
Ar

37.96272 g mol1
39.9624 g mol1

0.063%
99.600%

38

r
(i) 52 r Ar
(ii) 52 u He
(iii) 52 g He
r
r 3.38 g 0.690 g r
10.0L STP 11.69 g
(i) r
(ii)
(iii)
CaCO3 r HCl r CaCl2 CO2
s t s s
0.75M HCl 25 mL r CaCO3

r r (MnO2) r HCl r
r
s t s s
HCl

qrs

STRUCTURE OF ATOM

ttt ttttt ttt

(400

(atom)

atomio

(uncutable)

(i)

(ii)

(non-divisible)

26

(iii)
(iv)

(ebonite)
(fur)





r

PP

r

r

(deposition)

qst

r


r
r

qst qst

r




(TV

(i)
(ii)

(cathode rays)

27

(iii)

(iii)

(iv)

t rs

rs

(v)

(e)

(me)

e/me

= 1.758820 1011 C kg1

me

(C)

(2.1)
kg

q rs

(ii)

(i)

28

atomizer
condenser



r

X-


X-






(q)
(e)
q = ne n = 1, 2, 3...

P
qs tq q
t t qs q
q t t qs s
tt
(i)
qs t qs
qs tq q t
q s t t
(ii) qs t q t
t q t
(iii) t qs q q
sq
(iv) q t qs q
t qs

q t t t

q t qs q
qs s q t
s q t qs q q
qs q t q t
qs q t
q t qs t t t
qs q q t qs s s s

'e'

t q t 1.6 1019 C,
q tt t 1019C t
e/me t t t s q q
t q t (me) t q

s
q t s tq
sq s (sub-atomic) qs
t s s q qt
t s q
t qs q t
q q t t t
q q

= 9.10941031 kg

(2.2)

P
t t t q q s q
t 1010m
t t
t q q
q t

29

pudding)]
(watermelon)

(raisin pudding)

(plum

P P P

X-

qr

tq

sP

X-
X- qP P q P
(deflect) P q r P
P (penetrating power) P

qr q
P

qP qr P s

(wavelength)

Ps

(0.1 nm)

q P

q P
qr Henri

Becqueral 1852 1908

qr Pq q q P

Pq

(radioactivity)

P r
P qP P

r s
q q
P

P qr
P

q r

s
q

Roentgen, 1845-1923)
q r

(Wilhem

X-

qr q P

P P

P q r

qr s

PP

q r PP

qr q q P

(fluorescent)

P s

s P

30

(gold foil)


100 nm P
P

(fluorescent)

(flash)

t


(shot)

P
P
P
P
P
P
(i) P
P
(ii)

(iii) 1)
180


(i)


(ii)
(repulsive
force)


P

(iii)

q 1010 m
q 1015 m


P q
5 km
P P


(i)
P

rs

31

(ii)

(iii)

(orbit)

(A)

(Z)

(Z)

s t

t


tt

(Tritium,31T)

(Z)

q r

s tr r

t r

(n)

, Z = 35, A = 80,

nucleons

r s t r

(Z)+

t r

(n)

(X)

(A)

= 80 35 = 45

(Z)

= Z = 35

(S)

= 16

32

=
+
= 16 + 16 = 32

= (18 16 = 2)






= =



A Z
t

P

t
t (kq1q2/r2)
q1 q2 r
k

m1
r

m2 r t
G t
* t
t t


t
t t

(acceleration) t

t
t
qs t
qs t
t


(orbit)
P t
(spiral) t 108s

t qs t


P

t

t q
t


t
P s t
t q





t t



(i)
qs t

33

(ii)

P
P

(ii)

(iii)

t P

P P

quency) 106 Hz

(waves)

10 Hz
2

(radiofre-

(microwave)

q
rs q
rs r

(infrared) 1013Hz

(ultraviolet) 1016 Hz

corpuscles

Hz

1015

(visible)

(iv)

()

P P

()

()

SI

(Hz,s )

(m)

(i)

3.0 108 m s1 (2.997925 108 m s1)

34

(speed of light)
c ( ) ( )
(c)

c=

r r
( )
(wave number)

m1
cm1 SI
P

q

q

s q

(400 nm)
(750 nm)
9
(Hz) r (1nm = 10 m)

1,368 KHz
(transmitter)
r

t c
r r

= 7.50 10

14

Hz

14
= 4.00 10 Hz

4.0 1014
7.0 1014 Hz

35

(iv)

5800 A

( )

r r

r r r r

r r r
r r r r

r r r

r r r

r r r
r r

( )

r r r

P
s

r r r r

(black body)

r r

qt

r*

(diffraction) r

q
q

qt

qt

(exact)

r rr

r r

** (interference)

r r rr r

r r r

r r r

r r

r r

r r r

r r
r r r

r r

r r

r

(i)

black body radiation)

(ii)
(iii)

(discrete)

r r r

r r

r r

r r

(quantum)

(E)

E = h
*
**

( )

r r

36

(i)

(ii)

s q
ts
q
s q
sq (time lag) s
s s

r rr

(1858-1947)

P

(Institute of theoretical Physics)




P
qst ht
q 6.6261034 Js
s qt s
s q q q
qs s q

s t
s s
t t t
q q
s t s
q s
q q
s

r
r r r r
r r
r r r
r r
(iii)
t (threshold frequency)

s q q
s > 0 q s

q q qs qsq
s q q s s qt
q q
q q q s ts s s
q ss

s s q q q t
s q q s q
q t q
qs [ = (4.3 4.6) 1014 Hz]
ss t s
s t qs qs
= 5.1 5.2 1014 Hz q t

( 0) 5.01014 Hz

37

(1879-1955)
t P P

P P P

t P P

t P

PP P

P q r Ps

q s P P P

P q Ps P

P P r

W0

h0

(h h 0)

(conservation of energy)

me

5 1014 Hz

(E)

E =h

= 510

14

34

= 3.313 10

J s

E = (6.626 10

(2.7)

W0 /eV

h = 6.626 10

34

19

J s)

(5 10

14

Li

Na

Mg

Cu

Ag

2.42

2.3

2.25

3.7

4.8

4.3

s )

38

= (3.313 1019 J)
= 199.51 kJ mol

(6.022

1023 mol1)

400 nm

= 2.31 10 J mol

s r

P
= 517nm

= 100 = 100 Js1

= E = h = hc/

0, 7.0 1014 s1
=1.0 1015 s1
q s

300 nm r
q 1.68 105 J mol1
s r
s t r r
s
r

= 1.988 1019 J

300 nm (E)

-19
= 6.626 10 J

r
19

= 6.626 10

23

J 6.022 10

= 3.99 10 J mol

mol

r r s t
r
5

= (3.99 1.68) 10 J mol

mev2=h( 0 )

= (6.626 1034 J s)
(1.0 1015 s1 7.0 1014 s1)
= (6.626 1034 J s)
(10.0 1014 s1 7.0 1014 s1)
= (6.626 1034 J s) (3.0 1014 s1)

*

rr
rr
r r
(refract)
r
r
r
r q
r r

* discreat

39

(spectrum)

4 1014Hz

7.50 1014Hz

(continuous spectrum)

r
r
r

r
r

(spectroscopy)

q st q

q q qqqq

(slit)

40

r

(Rb), (Cs), (Tl),
(In), (Ga), (Sc)

(He)
P

P (Balmer
series)
t

r

s P

(2.9)

n1=1,2........ n2 = n1 + 1, n1 + 2......
109,677 cm1
(Rydberg constant) n1 = 1, 2, 3, 4

(Lyman), (Balmer), (Pashen),
(Bracket) (Fund)

t
H2
t


r


( ) q
s P

(2.8)


n = 3, 4, 5 ...

(i)
(ii)

41

r
P

(i)

(ii)

r r


r
t s

(v)


(angular
momentum) (I) ()
me
(r)

(m)

=I

P
q r s tt

I = m er

(iii)

= m er

v/r = mevr

= v/r

(iv)

'Atoms for Peace'

E2

E1

(2.10)

n = 1,2,3.....

(2.11)

h/2

42

n = 1,2,3...

(principal quantum number)



rn = n2 a0

(2.12)

t a 0 = 52.9 pm
52.9 pm
(n = 1)
n r

P

t n = 1,2,3....

(2.13)

t RH (Rydberg constant)
2.18 1018J
(ground state)

E1 = 2.18 1018 ( ) = 2.18 1018 J

n = 2 E2 = 2.18

1018J ( )= 0.545 1018 J.

n =
qr sq
n

n =

En




(rest)


n = E= 0

n En
n
= 1






He+ Li2+, Be3+


t



(2.14)

(2.15)

t Z

Z


t



t

43

ni > nf

r r

ii

E = Ef Ei

(2.16)

ni

nf

(2.17)

n=5

n=2

ni = 5 n f = 2

t s

(2.18)

s q

st

(2.18)

(2.19)

(2.20)

(2.21)

nf > ni

q r

= 6.9110

14

Hz

44

He

1
atom

He n = 1, Z = 2

n = 1 Z = 2
r

q st t t


He+, Li2+, Be3+



(i)
[ (doublet),
]







(ii)

P





( ) (p)

(2.22)

m v p

45

t
t

t t t

3.6 A t

t t

0.1 kg

10 ms

34

= 6.135 10

29

kg

3.0 10

25

25

kg

q
r

t t

(2.23)

x
p

(p )

x
v )
v
x

t t

9.1 10

m (J = kg m s )

P P

= 6.626 10

t
t

t

46

P

(trajectories)












r

(106 kg)

q

st

t
ss

v.x






9.11 1031kg

108m
v

47

18

10

t t

0.1

t t

qr

t t

7
1

= 0.57910 m s
6

= 5.7910 m s

2 2

(1J = 1 kg m s )

2%

40g

45m/s

t t

2%

t t

(quantum machanics)

48

r r
r
r r
r r
r
r r r r
r
r r r
r r r r r
r r r

rr r
r r r r
r r
r r
r r r
r

r
r r
r r
= E

r (operator)

r
r
r
r

r E
P

r r r
r r
r ()
r r rr

[ n (principal quantum number) l (azimuthal quantum num-

st t t
t
t t t
tt
t

tt

t t
t

t t
t
t
t t
t t
ml (magnetic quanber)

tum number)] r r
r
r r r
r r
r r
r r r
r

r r
(atomic orbitals) r
r
r r
r
r r
r r

(predict) r r
r r r
r
r r r r
r r q
r r r (exact)
q
r r r r
r
r r

r

49

r s s

(probability density)

qr st

t

s s

qr s

s
s

(probability)

s s

n, l

ml

'n',

t

s

He

, Li2+

(shell)

'n2'

= 1

............

= K

............

50

(n, l, ml )

r n st s s
s (n = 1) st s l
= 0 t st s (n = 2)
(l = 0, 1) n = 3 t (l = 0, 1, 2)
st s n r t
s q r (l )
t t s l t
rt t s
l


t (notation) s p d f g h ......
r q r l
t t s

2
2




2



2




P 'l'
(orbital angular momentum) q r
(subsidiary quantum number) st s s
t t s n
l 0 n 1 t n s t s
t n l 0,1, 2,....(n 1)
s t s
s n = 1 st s t l
0 st s n = 2 l 0 t
s t s n = 2 l 0,1 s
(subshells) t (sub-levels) st s r

(magnetic orbital quantum number) ml t

t s
ml 2l + 1 s
t s
ml = l, (l 1), (l 2) .... 0, 1 .... (l 2), (l 1), l

t ml s t
st s t 2(0) + 1 = 1 s t s
ml=1,0,+1 s t s [2[1]+1=3p

51

ml = 2, 1, 0, + 1
ml

+ 2

ml

nl = 2,l = 1, ml = 0

(i)

(ii)

nth

(2l +1)

(l = 0)

(l = 2)

(l = 1)

5d

t r

11

(iii) ml

(2l + 1)

(iv)

(ms)

n=3

(intrinsic)

(vector)

ms

ms

+ 1/2

1/2

(spin states)

1/2

ms

spin down

spin up)

+1/2

3s

0, 1

(n = 3, l = 1

n = 3, l = 2

=9

=1 + 3 + 5 = 9

ml = 0

t t

l =0

(n = 3)

(George Uhlenback)

(Samuel Goudsmit)

ms

r q

t r
r

ml

3d

3p

n =3,

ml = 1,0, + 1)

ml = 2,1,0, + 1, + 2

2
n

s,p,d,f

n 2, l 1

n 4, l 0,

n 5, l 3,

n 3, l 2

52

2p

4s

5f

3d

(coordinates)
r
[
1s (n = 1, l = 0) 2s (n = 2, l = 0)
]

qrs q
1s r 2s r r
r r q q

t

[
1s 2s r

1s 2s t
1s P

t t t 2s
t
t r
t

P (small maxima)
t
t
ns (n 1)
n
t 2s
3s

t
(dots)

1s r 2s q r
q r r

1s r 2s r q
q

(boundary surface diagrams) t

(contour surface)

t t

53

1s 2s

90%

4p > 3p > 2p

100%

n 2

100%

90%

1s

s
n

2s

4s > 3s > 2s > 1s

(lobes)

l=2

*r

(n)

2,

1, 0 + 1

+2

ml

2p

dz2

(4d, 5d, ---

dx y , dyz, dxz, dx2y2 dz2

n > 3

54

PP P
r
r


1s < 2s = 2p < 3s = 3p = 3d < 4s = 4p
= 4d = 4f < ...........
(2.24)

r qs t
t r
r
(degenerate)
r


(ground state) r
r
r
2s, 2p
r (excited state)

3d

np nd

pz xy
dxy z-
xy r
l
p d
r
(n 1) l
(nl1)

55

s, p, d, f ...

Zeff

(l )

(splitting)

(Ze)

n
l

(n + l )

(n + l )

(Ze)

(n + l )

(shielding)

(effective nuclear charge)

Zeffe

(Zeff)

2s

2s

(Z)

E2s(H) > E2s(Li) > E2s(Na) > E2s(K).

qrsrt

rr

rr

rr

(Pauli's exclusion principle),

(Hund's maximum multiplicity rule)

56

r r
r
(n + l)

P
q s t t
q s t

q
s s s t
t s

r
r
t s n,l s
ml s t
q
s
s qs
s t 1s q s
t 1s s
s t p s d s
s s t q
s t
n
2n2 r

r

r
s s t

s q
P s t q s

q s s
t
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d,
6p, 7s...

s t s s
q s t

57

(degenerate orbitals)

p, d

2s

qr

tqs

(electronic configuration)

1s2 2s2

2p

2p

(N, 1s22s22p3),

(C, 1s22s22p2),

(B, 1s22s22p1),

(ii)

sa pb dc

1s 2s

(i)

2s

1s

(Li)

(O, 1s22s22p4),
(F, 1s22s22p5),

(Ne, 1s22s22p6).

a, b, c

P P




P

1s

P

P

1s2

(He)

1s

1s1

1s

Na,

2s2 2p6 3s2 3p6)

1s22s22p63s1)

Li

Ne

3p

(Ar,1s2

3s

P P

(Ne)

58

(Na, [Ne]3s1), (Ar, [Ne] 3s23p6)

t
t
Ne Na Ar

(K) r (Ca) 3d
4s
r 4s

3d 4p

(Sc), (Ti), (V),
(Cr), (Mn), (Fe), (Co),
(Ni), (Cu) r (Zn) 3d
t
r 3d r


r r t p3 p6, d5,
d10, f7, f14
r r
d5 d10 r

3d (Ga) 4p
(Kr)
(Rb) (Xe)
5s, 4d r 5p
4s, 3d 4p r 6s
(Cs) r (Ba)
t
r (La) (Hg) 4f 5d

6p, 7s 5 f
6d (U)
r t




t

t
r
He r Ar

t




P P

r r t
r


Cu r Cr
t 4s r 3d
t s
t r
r t t
Cr r Cu
3d5, 4s1 r 3d10,
4s1 3d4, 4s2 r 3d9, 4s2
r

59

3d

P








P

energy)

(exchange

(half filled)

qrs

t t
t

t t

(i)

(iii)

(ii)

t t t

60

**

61

62

-















P

P

P


r n, l, ml







+
2+


r He , Li
n l
(n + l )
(n + l ) n

63

(i)

(ii)

(i)

(ii) 7 mg
(iii)

14

= 1.675 1027 kg

(STP)

34 mg NH3

(i)

(A)

(Z)

Z = 17 , A = 35.

(ii) Z = 92 , A = 233.
(iii) Z = 4 , A = 9.

() 580 nm

()

3 1015 Hz

(i)

(ii)

10

0.50

2.0 10

4 10 m

4000 pm

1J

2.13 eV

(i)

eV

(ii)

(iii)

(1 eV= 1.6020 1019 J)

242 nm

kJ mol

6800

(0 )

(W0 )

64

t t n = 4 t n = 2 t t
r t r
n = 5 H t
r t
t
n = 1 t
t t t n = 6 t t
r
(i) t t 2.18 1018 J atom1
t
(ii) t r t
t r r r
t
t t t
t r t t r
t r t 2.18 1011 ergs
t t En = (2.18 1018)/n2 J t
n = 2 t r t
r cm r t r t
2.05 107 m s1 r r
r r
31
9.1 10 kg rt t 3.0 1025 J
r r t

Na+, K+, Mg2+, Ca2+, S2-, Ar

() H
() Na+
(r) O2
() F
(ii) t
t
() 3s1
() 2p3
(r) 3p5 ?
(iii)
1
2
3
2
1
() [He] 2s
() [Ne] 3s 3p
(r ) [Ar] 4s 3d .
n g r
3d n, l ml t
(i)
(ii)
H2+, H2 O+2

(i) n = 3 l 2ml r
(ii) 3d
ml l
(iii)
1p, 2s, 2p 3f
(i)

65

s,p,d

n = 1, l = 0

n = 3; l = 1

n = 4; l = 2

n = 4; l = 3

n = 0,

l = 0,

ml =

0,

ms = +

n = 1,

l = 0,

ml =

0,

ms =

n = 1,

l = 1,

ml =

0,

ms = +

n = 2,

l = 1,

ml =

0,

ms =

n = 3,

l = 3,

ml = 3,

ms = +

n = 3,

l = 1,

ml = 0,

ms = +

n = 4, ms =

n = 3, l = 0

He+

n=4

n=2

He+ (g) He2+ (g) + e

20 cm

2.18

0.15 nm

1018 J atom1

2 10

2.4 cm

2.6

1.6 cm

2.5 1016C

1.282 1018C

79
35
Br
Br

31.7%

11.1%

66

%


(oven)
(amber)


X-

337.1 nm
5.6 1024
616 nm


2J

600 nm
3.15 1018J

2ns
2.5 1015

589 589.6nm

1.9 eV

500nm

P (nm)
v 10

(cm s )

500

450

400

2.55

4.35

5.35

0.35V
256.7 nm

150pm
1.5 107ms1

n n = 3 v = 3.29
1015 (Hz) [ 1/32 1/n2] 1285 nm

1.3225 nm 211.6
pm

67

s s ss s s
s s s
s s s s s s s

s

1.6 106 ms1

s s s s s s

s s
s s

800pm

s
s s

s s s s
s

2.9 106ms1

s s s

s s

1000 V

s s s s

4.37 105 ms1

0.1 kg

s s s s s

s s

0.002nm

s s

s s s
s s s

h/4m 0.05 nm

s s s s s

s s s s s s s s

1.

n = 4, l = 2, ml = 2 , ms = 1/2

2.

n = 3, l = 2, ml = 1 , ms = +1/2

3.

n = 4, l = 1, ml = 0 , ms = +1/2

4.

n = 3, l = 2, ml = 2 , ms = 1/2

5.

n = 3, l = 1, ml = 1 , ms = +1/2

6.

n = 4, l = 1, ml = 0 , ms = +1/2

s s P s ss s

2p

s s

3p

s s

4p

s s ss s s s s

s s s s

(i) 2s

Al

Si

3s, (ii) 4d
s

3p

4f

(iii) 3d

3p.

s s
ss s s

s s

ss

n=4

Si

Cr

Fe

Kr

s s s

s s s s s
s s

CLASSIFICATION OF ELEMENTS AND PERIODICITY IN PROPERTIES

r
r

t r r
r

t r

IUPAC
s, p, d

PsPPP P PPP P PPPPPP P

q
PP PP PP PsPP
q PPPs
P P sPP PPP PPPPPP
sP Pq P PPP PP P sPPPPPP PPP P
P PP P q

69

r rr

qssssq

qssssq

qssssq

Li

Ca

40

Cl

35.5

Na

23

Sr

88

Br

80

39

Ba

137

127

Ca

P t

(A.E.B. de Chancourtois)

t t

(curve plotting)

t
t

octaves)

(Law of

(eight musical note)

Li

Be

qssssq

11

12

14

16

19

Na

Mg

Al

Si

Cl

qssssq

23

24

27

29

31

32

35.5

Ca

39

40

qssssq

70

(Germanium)

r







P
(empirical formula)
r

r

r

VI VII








(Gallium)

r (Eka-Aluminium)
(Eka-Silicon)












qsqt q qq q
qq q q






X-
X- r Z
r P

P
r

68

70

72

72.6

/ (g/cm3)

5.9

5.94

5.5

5.36

/K

302.93

1231

E2O3

Ga2O3

EO2

GeO2

ECl3

GaCl3

ECl4

GeCl4

71

r rr

72

Tobalask

(Master's)
r
'Principles
of chemistry'




P

(1834-1907)




(observed)



r

(Ramsay) r (Krypton) r (Xenon)


(Accurate barometer)




(Mendeleevium)


(Glenn T. Seaborg)
P

P
P (Transuranic
Elements)

73

r rr

P n

t t t P

(The physi-

cal and chemical properties of the elements are

periodic functions of their atomic numbers.)

P P

(International Union of

Pure and Applied Chemistry)

q s

t P

t P

(periods)

(group)

P
t
t

IB...VII B,

IUPAC

IA...VIIA, VIII,

(Rutherfordium)

(Kurchatovium)

IUPAC

s P

root)

(numerical

(Sg)

IUPAC

I AVIIA, VIII, I BVII B

74

r
r

75

r rr

IUPAC

0
1
2
3
4
5
6
7
8
9

nil
un
bi
tri
quad
pent
hex
sept
oct
enn

n
u
b
t
q
p
h
s
o
e

(root)

un, bi

nil

IUPAC

(ium) t

IUPAC

(symbol)

IUPAC

Unbinilum

Ubn

IUPAC

IUPAC

Unu

Mendelevium

Md

Unb

Nobelium

No

Lawrencium

Lr

101

Unnilunium

102

Unnilbium

103

Unniltrium

Unt

104

Unnilquadium

Unq

Rutherfordium

Rf

105

Unnilpentium

Unp

Dubnium

Db

106

Unnilhexium

Unh

Seaborgium

Sg

107

Unnilseptium

Uns

Bohrium

Bh

108

Unniloctium

Uno

Hassium

Hs

109

Unnilennium

Une

Meitnerium

Mt

110

Ununnilium

Uun

Darmstadtium

Ds

111

Unununnium

Uuu

Rontgenium*

Rg*

112

Ununbium

Uub

113

Ununtrium

Uut

114

Ununquadium

Uuq

115

Ununpentium

Uup

116

Ununhexium

Uuh

117

Ununseptium

Uus

118

Ununoctium

Uuo

IUPAC

*
*

76

r r
r

P q 4p

q 3d

(energetically) q

(n)
(shell)

s, p, d, f




P P

P n P
(successive
period) qs t n=1, n=2
P


(n=1) P (1s)

(1s1) (1s2)
K q q
(Li=1s2,2s1) 2s
P
(1s2,2s2)
P P P
q
L
q q

3s
3s 3p

(n = 4) 4s

3d
(3d transtitian series)
(Scandium : Z = 21)

3d1 4s2 3d
q
4p
(Krypton)
P
4d
(ytrrium, Z=39) 4d (4d transition
series) 5p

(Xenon)
6s, 4f, 5d 6p
4f
(cerium, Z=58) q (Lutetium,
Z=71) 4f

(Lenthanoid Series)
(n=7)
7s, 5f, 6d 7p
(artificial methods)

q
P
(Actinium, Z = 89) 5f
5f
(5f inner transition series)

(Actinoid Series) 4f 5f
P

77

r rr

s,p,d f

n=5

4d, 5s 5P

l=0,1,2,3

5s<4d<5d

ns1

qs

s,p,d, f

s-

(H=1s1)

t

t

t
t

(valance shell)

(He=1s ),
2

(Aufbau Principle)

(vertical columns)

(Group)

(family)

ns1

ns2

Li

1s22s1 [He]2s1

11

Na

1s22s22p63s1 [Ne]3s1

19

1s22s22p63s23p64s1 [Ar]4s1

37

Rb

1s22s22p63s23p63d104s24p65s1 [Kr]5s1

55

Cs

1s22s22p63s23p63d104s24p64d105s25p66s1 [Xe]6s1

87

Fr

[Rn]7s1

78

79

r rr
10

d-

s-

d-

p-

s-

(Representa(Main Group

ns2, np 1

P P

tive elements)

p-

Elements)

f-

p-

ns2, np 6

ns2 , np6

(90Th

(n1)d

14

ns ]

01

Lr)

103

(58Ce

Lu)

72

[(n2)f 1

f-

s ts

s s

(Halogens)

(Chalcogen)

electron gain enthalpy)

(negative

(Radioactive)

(Nenogram)

q q
q

d-

110

02

s
s

At

14
10
2
5

[Rn] 5f 6d 7s 7p

Zn, Cd

Ra

[Uuo] 8s

80

r s-,p-,d r f-
r r r r
r r r r
rr r r
r r r r
r [
r 303K 302K ] r
r r r r
r r r
r r r
r r t r r
r r r
P r r
r r
r r r
r r
r r r r
(Brittle) r r r r
r r
(abrupt) r r
(Zig-Zag line) r
r r r
r r
r r r
r r (Metalloid) r

r r
r r r r
r r
r r r
r
r
r r
r
r r t
r
r r r
r t
r r r
rr

r
r rr
r
r

r r
r r r r
r
Si, Be, Mg, Na P

r
r P r r r
r
r r

qs

r r

r
r r
(Ionization Enthalpy),
(Electron Gain Enthalpy)
r (Electronegativity) r P

r
r
t r r
r ( 1.21010m) r
(electron cloud)
r r
r r r t
r

r t

81

r rr

(Single Bond)

(covalent molecules)

(covalent

Radius)

pm

(Metalic Radius)

pm

(bond length)

distance)

(Internuclear

pm

pm

(Atomic Radius)

x-

(valence electron)

pm

(n)

II

III

q st s t s ts

(pm)

Li

Be

152

111

88

77

74

66

64

Na

Mg

Al

Si

Cl

186

160

143

117

110

104

99

q st s s ts

Li

152

64

Na

186

Cl

99

231

Br

114

Rb

244

133

Cs

262

At

140

17

82

qs t

qs t

(parent atom)






(F ) 136 pm
pm
pm Na+
95 pm

(Isoelectronic
species)

2

+
2+
2
O ,F ,Na ,Mg ,O

PP


2+

3+

Mg, Mg ,Al, Al

Mg
3+
Al

r

83

r rr

(Ground State)

(Isolated Gaseous Atom)

(X)

X(g) X+(g) + e

(3.1)

(kJ mol1)

3.5

qs

X (g)

2+

X (g) + e

(3.2)

(i)

(ii)

(core elctrons)

(Screened)

(shielding Effect)

Effect)

(Specified)

(maxima)

(Screening

(Effective Nuclear charge)

(Actual Nuclear charge)

1s

2s

(closed electron shell)

(curve)

(shielded)

(Minima)

ns1

(Inner Core Electrons)

(compen-

84

qrs
qrs

Fig. 3.6

sate)

t


t


t

t (Z = 5)
(Z = 4)


t s p

s

p
2s (penetration) 2p

2p
2s
(Shielded)
2s

2p





2p
p
t 2p 2p
2p

2p
t 2p
t

Na, Mg Si
P
k J mol1
kJ mol1
t

85

r rr

qs t

k J mol

3p

3s

(anion)

t P
P

(X)

P
P

P P

P t s
s P

P P
t
P
tqs

s

X(g) + e

(3.3)

P t P

P
P

(exothermic)

X (g)
(endothermic)

P t

P t

P P

P P

P P

t t P

t
P

eg H

n = 3 S Cl

16

eg H

73

Li

60

141

Na

53

200

48

Se

Rb

47

Cs

46

(n = 2)

17

eg H

(kJ mol1)

eg H

He

+ 48

328

Ne

+ 116

Cl

349

Ar

+ 96

195

Br

325

Kr

+ 96

Te

190

295

Xe

+ 77

Po

174

At

270

Rn

+ 68

(Electron Affinity) (Ae )

86

(space)


P,S,Cl F

3p

2p

Li F
F At














q

st

87

r rr

(

II)

Li

Be

1.0

1.5

2.0

2.5

3.0

3.5

4.0

III)

Na

Mg

Al

Si

Cl

0.9

1.2

1.5

1.8

2.1

2.5

3.0

( I)

( 17)

Li

1.0

4.0

Na

0.9

Cl

3.0

0.8

Br

2.8

Rb

0.8

2.5

Cs

0.7

At

2.2

OF2

Na2O

(diagonal relationship),

(Inert pair effect),

lanthanoid contraction)

(effect of

F>O>Na

2s22p5

-1

2s 2 2p 4

+2

Li

q st

(Representative Elements)

P
P

3s

+1

P
P

(Periodic Trend)

88

13

14

15

16

17

18

3,5

2,6

1,7

0,8

(Variable
Valency)





(prediction)

q r
r
r r s
r
r


t

(Diagonal Relationship)

r
r
r


2s 2p
t
(3s, 3p, 3d)

[BF4] r


[AlF6]3

LiH

NaH

CaH2

13

14

B2H6

CH4

NH3

H2O

HF

AlH3

SiH4

PH3

H2S

HCl

GeH4

AsH3

H2Se

HBr

SnH4

SbH3

H2Te

HI

KH

15

16

17

Li2O

MgO

B2O3

CO2

N2O3, N2O5

Na2O

CaO

Al2O3

SiO2

P4O6, P4O10

K2O

SrO

Ga2O3

GeO2

As2O3, As2O5

SeO3

BaO

In2O3

SnO2

Sb2O3, Sb2O5

TeO3

PbO2

Bi2O3

SO3

Cl2 O7

89

r rr

M/ pm

n+

152

111

88

Na

Mg

Al

186

160

143

Li

Be

76

31

Na

Mg

102

72

/ pm

t qs

qs

t t

2+

Al [Cl(H2O)5]

state)

(oxidation

+3

Cl2O7

Na2O

p p
(t C = C, C C, N = N, N

C = N, C N),

Be

Li

Al2O3, As2O3

CO, NO, N2O

(amphoteric)

t
t
t

t t

qs
s t

Cl2O7

Na2O

Na2O

Cl2O7

2Na + H2O

2NaOH

Cl2O7 + H2O

2HClO4

90

3d

4f s-

P
P P
q rs t q
q P r (Valence Shell)
q r P
s (Valencies) P
P q s- t p- t d- f-
1s P
r
r t r
t P t (Semi metals) (Metaloids)

Si, Ge, As q P q
q P q P P

P t t t
q
s q

q P
P
r P
r q q
P r s q P
P t P
t

91

r rr

Z=14

(i)

(ii)

(i) F

(ii) Ar

(iii) Mg2+ (iv) Rb+

N3, O2, F, Na+, Mg2+ & Al3+

P
P

J mol

2.18 1018J

P Li< B<Be<C<O<N<F<Ne

(i) O

(i) Be

i H , N

i H ,

P
P P
P

92

A1

801 577

Ga

In

T1

579

558

589

(KJ mol1)

r
(i) O F
(ii) F Cl

s
N


(i) t
(ii)

r


t
P P q

17
F>Cl>Br>I
s, p, d f
r
(i) ns2 np4 n=3
(ii) (n1) d2 ns2, n=4
(iii) (n2)f 7 (n1) d1 ns2, n=6

(egH) (kJ mol1 r

H1
H2
egH
I
II
III
IV
V

520
419
1681
1008
2372

7300
3051
3374
1846
5251

60
48
328
295
+48

(kJ mol1

93

r rr

VI

738

1451

40

MX2 (X =

(binary halide)

MX X =

(n)

(Z)

F, Ne

Na+

(Z)

PP

(n)

94

n n

B, Al, Mg, K

B, C, N, F Si

F, Cl, O N

P
P

CHEMICAL BONDING AND MOLECULAR STRUCTURE

s, p
d

qr r
st r s
s

96

ss s s s s
s s
s
s s ss s
s s s (Valence)
s
s s s
s P s s s
s s s
s s s P s s s
s s ss s s s s s
s s ss s s s
s s s ss
s s s s ss
s s s s
s s
P
s s s s
s s s s s
s
s s s
s s
+
s (Na )

s (Cl ) s s s
Cl2, H2, F2, s s s s
s
P ss s
s s
s s s s s s
s s s s s s s
s qrt (Valence Electron) s
s s (Inner Shell Electron)
s s s s s
ss s
s s s s s s s s
ss s s
(Lewis Symbol) s
s s s

s s s
s s s s s
s
s s s s
s s s s
s s s s s s
ss s s

t t r t tt
t
s s ss
s s

s s s

ss s s s
s s
s s ss s
s
s
s s s
s s s ss
2
6
ns np s s s
s s s
s s s s s s

s
s s
s s NaCl s

+

Na
1
[Ne] 3s
Cl + e

Na + e
[Ne]

Cl
2

[Ne] 3s 3p
+

Na + Cl

[Ne] 3s 3p [Ar]
2

NaCl Na Cl

CaF2
2+

Ca
2
[Ar]4s

F +e

[He] 2s 2p
Ca

2+

Ca + 2e
[Ar]

+ 2F

[He] 2s 2p [Ne]
2

CaF2 Ca (F )2
2+

Bond)

(Electrovalency)

(Electrovalent

97

Cl Cl

(Postulates)

(Sharing)

Cl2

[Ne]3s 3p

(Covalent Bond)

(Cl2)

q rst

sq

(Octet Rule)

(Single Covalent Bond)

(Multiple Bonds)

q q t

Bond)

(Double

98

(Ethene)

CH4

C2H4

t t
t t N2 t

(Skeletal Structure),

q
q q (Terminal Position) NF3

N2

C2H2

PP P P
P
t
r
t
qs
(Formation)

q

q

99

N(2s 2p ), O (2s 2p )
5 + (2 6) = 17
*

P P
P

qrsts

17 +1 = 18

CO

NO2

ONO

2s 2p

2s 2p

CO

CO

= 4 + 6 = 10
r

100

(Isolated)



t
qr q
q sr q
q q P

P
P
r sr
q

P




(O3) O3
t

t
O

O3
t

t




t LiCl, BeH2
BCl3

Li, Be B

AlCl3 BF3
(Odd-Electron)
(Odd)
t
NO

NO2

(Expanded)

3s 3p 3d

MX(s)

ing)

(Coulombic Interaction)

NaCl

(Pack

(Lattice)

qs

XeF2, KrF2, XeOF2

eg

(Electron Affinity)

X (g) ;

M (g) + X (g)

M (g) + e ;

X(g) + e

M(g)
+

PF5, SF6, H2SO4 r

(Expanded Octet)

101

102

+
Na Na 495.8
1

kJ mol Cl(g) Cl (g)

1
348.7 kJ mol
147.1 kJ (Value)
(788 J)



P

tqr s tqr t


P
NaCl
1
788 kJ mol
+

NaCl Na (g) Cl (g)

788 kJ

AB
R = rA + rB R rA rB
A B

q


(Electron Diffraction)

rvdw rc

stt

HOH

stt

tt t ttt ts tt

t t

103

ss t

t t

(pm)

OH
CH
NO
CO
CN
CC
C=O
N=O
C=C
C=N
CN

96
107
136
143
143
154
121
122
133
138
116

CC

120

stt

t t

t t

t t

tt

(pm)

H2 (H H)
F2 (F F)
Cl2 (Cl Cl)
Br2 (Br Br)
I2 (I I)
N2 (N N)
O2 (O = O)
HF (H F)
HCl (H Cl)
HBr (H Br)
HI (H I)

kJ mol

HH

435.8 kJ mol

H2(g) H(g) + H(g); aH = 435.8 kJ mol

N2

O2

stt

74
144
199
228
267
109
121
92
127
141
160
s

s t

tt

* rcov/(pm)

O2 (O = O) (g) O(g) + O(g);

1

H = 498 kJ mol

N2 (N N) (g) N(g) + N(g);

H = 946.0 kJ mol

HCl

HCl (g) H(g) + Cl (g); aH = 431.0 kJ mol

H2O

OH

104

H2O(g) H(g) + OH(g); aH1 = 502 kJ mol

OH(g) H(g) + O(g); aH2 = 427 kJ mol

H
O H
O H
C2H5OH



P
O H

1
= 464.5 kJ mol

(Bond Order) H2
q r O2
q N2
q st r
CO r
q r
N2 aH 946
1
kJ mol r


F2

N2, CO NO+




(Parameters)

P

I II

O [ I II
(Canonical) III
(Resonance Hybrid) ]
O O
O = O O O
st 148 pm 121 pm
O3 O O
128 pm t O3
r
t I II
O3
O3
(Resonance Concept)





(Canonical)

(Resonance Hybrid)
t O3 I
II
III

105

stt

CO3

(I, II,

O3

III)

I, II

III

CO2

110 pm

(C = O)

CO2

CO2

121 pm

H2, O2, Cl2, N2

F2

CO2
(I, II III)

HF

CO2

III

(C O)

(115 pm), (C = O)

115 pm

(C O)

I II

CO2

r P

CO3

st

I, II,

r PP P PP r q

rPP

III

HF

106

(Dipole
Moment)






X-




() = (Q)
(r)
(Debye)
(D)
30

1D = 3.33564 10

Cm

C m









HF

(Vector sum)

O H 104.5

30

6.17 10 Cm [ID = 3.33564

30
10 Cm] OH

= 1.85 D
30

= 1.85 3.33564 10
30

= 6.17 10

C m

Cm

BeF2

(Cancel)

P s

BF3

B F 120

rt

)= 0

BF3

NH3 NF3



NH3

(4.9 1030 Cm) NF3

30
(0.80 10
Cm)

NH3

107

NF

NF

NF3

(Fajans)

(n 1) d ns

ns np

qrsP

(AB)
HF

1.78

HCl

1.07

HBr

0.79

HI

0.38

H2

(AB2)
H2O

1.85

H2S

0.95

CO2

NH3

1.47

NF3

0.23

BF3

(AB3)

(AB4)
CH4
CHCl3
CCl4

1.04

108

t

t
t
r (Sidgwick and Powell)
t r P
P
(Nyholm and Gillespie)

q s

t r P t t

t r
P
r (Electron Cloud)

r P
t

t t
r P (Spherical)

r P
r P
P t

t
r

q
s

P P > P P >
(lp)

(lp)

> P P
(bp)

(bp)

(lp)

r P
P
r r P
(Localised) t
P t
r P
P r
P P P P
P

t
r

t
(i)
s s s

s s
P A
r P AB


t P

(Distortion)
t AB2, AB3, AB4,
AB5, AB6
A r P B


BF3 (AB3), CH4 (AB4)
PCl5 (AB5) t
(Ball-stick) r

(ii)

(lp)

109

110

()

111

AB2E

V-

120

AB3E

119.5

109-5

AB2E2

107

109.5

104.5

112

P
P

PP P P P
P
P

P P
qrsPP

PP P
PP

AB4E

90



90





(Folded)

AB3E2

ClF3
T-

(Bond Dissociation Energies)
1
t
H2 (435.8 kJ mol , 74 pm) F2(150.6 kJ
1
mol , 144 pm)

Mechanical)

(Quantum

113

(Molecular Orbital Theory)

(Heitler and London)

(Variation)

NA

eB

eA

NB

(i)

NA eB, NB eA

NA eA, NB eB
(ii)

H2

(H2)

(Superposition)

(Pauling)

74 pm

(i)

(ii)

st

e A eB

N A NB

114

H2
435.8 kJ

1
H2(g) + 435.8 kJ mol H(g) + H(g)

t s CH4, NH3
H2O r t s t
r s
s s

H2 H

H2
P

q r s t
s s r
s s ss
s
t t
s r s t t t t
t s
r s t t t
s s (Spin)
ss

t r s t s t
s
t s (amplitude)
r s r s s
s r
s s
t t
t
t t s r
s s
p s s
r

s t s
s t r

t r s 1s
s
CH4, NH3 H2O t s
t t s
r CH4
s HCH t
10928' NH3
s

s p
P

115

(Head on)

CH4, NH3

H2O

[He] 2s 2px 2py 2pz

90

CH

2s

HCH

109.5

NH3

H2O

90

H2O

(i)
(i)

()
()

90

s-p

HNH

p-p

p-

s-

(ii)

qrs

p-

HOH

107

NH3

PP

PP

()

PPP

(ii)

qrs

(Half Filled) s-

CH

CH4

90

1s

2p

PP

1s

104.5

CH

CH4

HCH

t
t

ss

[He] 2s 2p

(CH4)

(Ground State)

(axial)

116

CH4, NH3, H2O

2s 2p
sp3

P






(i)

(ii)

(iii) q
(iv) rs
r
rs
t
s, p d

(I) sp s p
sp
z- sp
s pz sp
50% s- 50% p-

sp

sp
z-
s

sp
2
BeCl2 Be 1s
2
2s q 2s 2p
Be r (Promote) 2s 2p
sp 180
sp 2p
Be Cl

2
(II) sp s
p sp2
BCl3
2
1s
2
1
2s 2p q 2s
2p
2s

s p sp

BeCl2
2p sp2

2p
B Cl BCl3

Cl-B-Cl 120

117

NH3

H2O

NH3

sp

sp

1
x

sp

1
y

1
z

2s 2p 2p 2p

sp

sp

BCl3

p-

1s

sp

NH3

107

109.5

CH4

s s

(III) sp

NH

sp

25% s-

sp

sp

sp

2s

2p sp

75%

sp

109.5

sp

NH3

sp

104.5

sp

s, px, py

pz

109.5

PP

CH4

H2O

V-

118
3

sp , sp r sp

C2H6 sp
sp3 sp3
3

3
3
3
sp sp sp

sp3 1s
sp3s
C C 154 pm CH
109 pm
2
C2H4 sp
sp2
C C
sp2
2
sp s
2px 2py

(Sidewise)

P

CC sp2sp2

pm p-

CH (sp2-s)
pm HCH HCC
117.6 121


C2H2 sp
sp 2py
2px

qst -

119

dsp2

d+s+p(2)

[Ni(CN)4]2,
[Pt(Cl)4]2

sp3d

s+p(3)+d

PF5, PCl5

sp3d2

s+p(3)+d(2)

BrF5

sp3d2

s+p(3)+d(2)

SF6, [CrF6]3

d2sp3

d(2)+s+p(3)

[Co(NH3)6]3+

sp

C C

t t

sp

1s

4s

s, p

(i) PCl5

3s

qs

sp d

sp d

PCl5

sp d

p
d

(Z = 15)

d

3s 3p
4s, 4p 3p
4s 3p, 3d

d-

ss

2
z

3d

q tq

120

PCl5
3
sp d
P Cl
P Cl
120
(Equatorial) P Cl

90 (Axial)



PCl5

(ii) SF6 sp d SF6
3s2 3p4
3

s
p d
3 2
sp d

S F
SF6
P

st

P

(i)



(ii)
P
(iii)





(iv) P





(v)
P

(vi)




(vii)

SF6 qr

P
P ()
P (Amplitude)
P
P

1s

H2

structive)

= A + B
*
= A B

(*)

terference)

()

qq

qq

(Con(In-

(Destructive)

qr

t q

q qqr q q q

(Nodal Plane)

qq

qq

(Linear Combination of Atomic

Orbitals, LCAO)

(Approximation)

121

PP

PP

qr stqq

qq

st

stqq

qqr

1s

PP

PP

1s

2s

122

P 1s PP 2pz PP 2px PP
P PP P qP st
2s 1s

z-

r

2px

123

2pZ

2pZ

2py

z-

2px

2pz

1s

2pz

1s*

1s

1s

1s

2py

2py )

Li2, Be2, B2,

2s

2pz

2px

2py

t P P
t

P s

Na

(i)
(ii)
(i)

Nb

(ii)

Nb > Na
N > N
a
b

(Bond Order)

2p

B2, C2, N2

< *2px= *2py) < *2pz

1s < *1s < 2s < *2s < ( 2px = 2py) < 2pz

O2, F2

2py

*2pz

1s

1s < *1s < 2s < *2s <2pz<( 2px =

< *2px= *2py)< *2pz

C2, N2

2s, 2pz,

2px,

2s, 2pz, 2px, 2py

124

Nb > Na

(Nb < Na) (Nb = Na)


t
t

tt
t


(Diamagnetic)
P

(Paramagnetic)
P


q r

s (H2) qt
t qt 1s
q t
t 1s qt

2
H2: (1s)
qt
t

qt q t
t
qt t t 438 kJ mol1
74 pm
qt

(He2)
2
1s
He2
1s 1s
t He2
2
2
He2 : (1s) (1s)

He2

t Be2 [(1s)2 ( 1s)2
2
2
(2s) ( 2s) ]
3. (Li2)
2
1
1s 2s
Li2

KK (2s)2
t t KK, K

He2

Li2 P

Li2


P Li2
t

4. (C2) :
(C2) 12

C2

C2
P
C2 C2
.


N2 t

5.

125

(O2) :

16

O2

1s 2s 2p

O2

*2px

*2py

P x P P

O2

10

B2 Ne2

B2

Ne2

4.21

126

HF



P P P




t
qr
s qr
qr q
(F,O N)

'X'
'X'


X

(i)


(ii)

(i)


HF


(ii)

(F,O,N)

o-

'X'

4.22 o-

127

P
P r

qs

Pr

Pr

P P P P r

C2H2

C2H4

Be, B, C, N O

VB

1s

CH4, NH3 H2O P

lp-lp > lp-bp > bp-bp

H2

sp, sp , sp

BeCl2, BCl3,

128

t (F, N, O)

Mg, Na, B, O, N, Br.

S S2, Al Al3+, H H

H2S, SiCl4, BeF2, , HCOOH



BeCl2, BCl3, SiCl4, AsF5, H2S, PH3

P
PP
P

t NH3 H2O



s q
r
P H3PO3
H3PO3

129

SO3, NO2 r

CO2

rr

Ca

H2O

O Al

r r

H2 O

CO2

qr

LiF, K2O, N2, SO2, r ClF3

CH3COOH

r r
t

BeH

NH3 r NF3

CH4

r r t

CH4

BeH2

sp, sp

sp3

Al

C2H2 C2H4

x-

C2H4 r C2H2

1s

1s 1s

2px 2py

2py 1s

2s

130

CH3CH3 CH3CH = CH2
CH3CH2OH CH3CHO
CH3COOH



H2

Be2




PCl5

STATES OF MATTER

rtrr q
qrqrrs ts trq r
r

r
s

t
r

r
r

rr

rr

srqrqq
ts sqrqrr rrrrsq rts rrsrrrs s qrrqrrs rs rstr rr rsrtrsrrt rr ts

rrrrr rrr rs rt rs rrr rt rr

r
tr ts s r r t s rr
r
t
s

r
r

rr
r

t
s

r
r
r

t
s
r

r srs rrs rr
rrrs rtts r rrrqrs rsr rr tr tsr
r
s

r rrrr rrqs qrrt qrr r r rr r q r

r s rr rs s qrr rrsq r rrs qr rr rr tq
rqr
qr

r
r

r
r

r
r

r
s

qst
r rs tq
r qtrs r rrrr
rqrrs rrrrqr
qr

r
r

t
s

r
r

r
s

rqq
r qqrr qr s rrs s
t
q

s
rt
s

tr
rr rr rr r
H2O

132

P
P qr st r
st












A B
A


A

B
B

A B

P P
q P q P

1/r 6 r
~500 pm









()
(1.6 1019C)

133

HCl

1/r3

1/r 6

NH, OH HF

Cl

N, O F

kJ

mol1

P P

HCl P P

HCl q
rq
ss P

1/r6

(Cloud)

(Interaction)

134

q r
s t t
t

P P

XII

135

qr st
st r s r t

k1

k1

pV = k1

(5.3)

(5.1)
(5.2)

p1

V2

V1

P2

p1V1 = p2V2 =

(5.4)
(5.5)

k1

(Graph)

rt

V p

5.1, 300 K

CO2

136

300 K 0.09 CO2

/
104 Pa

2.0

112.0

2.5

89.2

11.2

22.30

3.5

64.2

15.6

22.47

4.0

56.3

17.7

22.50

6.0

37.4

26.7

22.44

8.0

28.1

35.6

22.48

10.0

22.4

44.6

22.40

103 m3

p r 1/V r
r r
r r
r r
r
r
r r r
r r
r
r r r r
d, r V r m

r r
r r

r r r r
r r

r r
r bar
r r r P
bar L r r r r
r r r

p1 V1 = p2 V2
p1 = 1 bar r V1 = 2.27 L

(1/V )/
m 3

pV/
102 Pa m3

8.90

22.40

p2 = 0.2 bar r

bar r
PP L r r
r
qst s
r r r

r r
r r r r r r
r
r r 0 C r r

r r 0 r t C

r V0 r Vt r

(5.6)

r r
r r tC Tt = 273.15
+ t r 0C T0 = 273.15 r
r
(Absolute Temperature) r

137

00C;

k2

P P

273.15
t

Tt = 273.15 + t

T0 =

(5.7)

273.15

(5.8)

273.15 C

s s

q
r

= k2

(5.9)

solute Zero)

(Ab-

V = k2 T

(5.10)

C P

2L

V1 = 2 L

T2 = 26.1 + 273

T1 = (23.4 + 273) K = 299.1 K

= 296.4 K

(C)

138

t
P

q
r

V n n
V = K4n

(5.11)

6.0231023





(STP)* 273.15 K 1 bar
Pascal STP
22.7 L mol1

K bar (STP)

s K







t

(5.12)

m =

(5.13)

* STP STP 0 Bar STP

1

Litre mol

STP
(SATP)
K
Litre mol1
Bar Pascal STP
K

139

(5.14)

Litre mol

VT

Vn

(5.15)

p2

= 8.20578 102 L atm K1 mol1

(5.18)

V1

(5.17)

T1

p1

T2, V2

(5.16)

(5.19)

0C

1Nm = 1J

pV = n RT

STP

= 8.314 J K1 mol1

= 8.314 102 bar L K1 mol1

= 8.314 Pa m3 K1 mol1

STP

qrst rss t

bar

PP

n, R, T

p, V

25C

10C

mm (Hg)

mL

mL

140

p = p1+p2+p3+...... T, V

p1 = 760 mm (Hg), V1 = 600 ml

P p r P p1, p2,

p3 r P

T1 = 25 + 273 = 298 K
V2 = 640 mL, T2 = 10 + 273 = 283 K

(5.23)

P
P P P
P r r r
P
r P P
P
p = p
(5.24)

p2 = 676.6 mm (Hg)

P P

P P

(5.20)

P d P

(5.21)

P
q
rs t P

(5.22)

P r r
r
P r
P P

T
V r
p1, p2, p3 P q P


(5.25)

(5.26)

(5.27)

P n1, n2, n3 q P
p = p1 + p2 + p3

= (n1 + n2 + n3)
(5.28)

p1 p P P

P n = n1 + n2 + n3
x1 P P P

141

p1 = x1 p

p2 = x2 p

p3 = x3 p

pi = xi p
t

pi

(5.29)

xi , i

bar

= 2.21 mol

= 8.375 mol

qs

= 0.21 25 (bar) = 5.25 (bar)

= 1 0.21 = 0.79

= 0.21

= 0.79 25 (bar) = 19.75 (bar)

142

pV p
pV
pV p
r 5.8, 273
K

qs t pV p qs
q

pV p



pV


pV

pV = nRT

143

q
t


r

(i)

(ii)

P t
P

t



t

(V nb)

t t

nb

P t

q t

(5.30)

(5.31)

t
t

t t

144

Z
p, V nRT

(5.32)

Z = 1
pV = nRT Z p

Z

Z 1

Z > 1
Z < 1 t
P

P t
q

r


s s P
r
Z


Z
Z

Z



(5.33)

(5.34)

145

30.98C

73

E 73

30.98C

(Tc)

(Vc)

(pc)

qrs r s qr s

21.5C

t
t

t t

V2

V3

p2

30.98C

p3

31.1C

t t

146

K rK
K

qs ts


































bar

bar

100C (373K)
99.6C (372.6K)

147

(Surface Tension)

qrr s qr r

rrs

Jm2

kgs2

SI

Nm1

148

t t
t
t
(Fire-polishing)


t
t
t t
t

t
t


t

tt t
t
t


t t

t
t
t tt
t
t
t
t

t

dz du

qrs


P
F A A P

t
t
P
SI
(Nsm2), Pas CGS
t
t t
1 poise = 1 g cm1s1 = 101kg m1s1

t
t


t t

t
t t
t

149

p ,V

p ,V
2

nRT

pV =

bar

dm

dm

bar
mL

mL

bar

bar

bar

bar

bar

150

C dm

C r bar r bar L
r r
C bar g dm STP

C bar mL g

C

C
bar dm mol r
(R = 0.83 bar dm mol
g r r
r

C dm r r

C m P
bar kg r r
= gm m R = bar dm mol
C bar CO2 r
R = 0.083 bar L mol1

2.9 g 95C 0.184 g r 17C

bar r r % r r
r
pV 2 T 2/n SI
C
C C

THERMODYNAMICS

U
U

U, H

H
H

( G)
G

P

t
P

rqr srrq q r rsr qq r qsr r s r rqsr
s rr sr r q
sr

qr

qr

q r r r sr
qrsqrsr r qr
q rqr qr r r

r sr rqssr qr rsr sr sqr rr r r qrsq

q qr q r qr q qr
r r sr s rr s q

qr
q

q qr qq sr q rsr r
qqr sr s sqrs srs qsqr r qs r r r r
r

r q r r qr

sr

q
r

r r q s
qr r r q q qs

152

t

P
t
P
P
+ = P
t P

P



t
A B
t *

(Boundary)
t


t

(Open System)

Exchange
t
(Closed system)

(Isolated system)

t

qrs



(Cartesian coordinates) (set)

qr

*

153

(p)

(Composition)

(V)

(T)

(Specify)

(Adiabatic)

PP

PPP

PPP

(n)

(p),

(V),

p, V, T

(T),

kJ

TA

UA

TB

UB

T = TBTA

TB > TA

U= UBUA

P P

(Immersion Rod)

(kJ)

TBTA

154

U,

wad U
U = U2 U1 = wad

wad
wad


V, p T

25C 35C 35C
25C = +10C 35C
(Degree)
(35C)
T








q





TA
TB
q TBTA

U = q

q

q
P

(6.1)
U = q + w

q w q + w =
U


w = 0 q = 0, U = 0
U = q + w,

P


q
r s



(Absolute) t
t
U

155

(i)

(w)

(ii)

(iii)

(i)

U = wad'

(ii)

U = - q,

(iii) U = q - w

qr t

= pex . A

Pex

w = x = pex.A.l
= pex . (V ) = pex V = pex (Vf Vi )

(Convention)

pex

Vi

pex

Vf

(Vf Vi )

(6.2)

= l A = V = (Vf Vi )

dV

156

( 6.3)

P P pex = pin dp
P Pq pex = (pin + dp) r
st P Pq


(Reversed)





P r r Pq P
P r q
Pq
P
t
Pq

dp dV Pq

(6.4)

q pin q
Pq
q n r (pV = RT)

= 2.303 nRT log

(6.5)

q (pex = 0)
P Pq q P
P P t P
r
P
Pq
w = pexV

pV Vi Vf



pex (pin + dp) P

157

U = q - pexV

U = qV , q V

(Subscript

(V = 0)
)

T=

w=0

pex= 0

q = 0

P P PP

U=0

(U = q + w),

U = qp-pV

q = w = pex (Vf Vi )

= 2.303 nRT log

U2U1 = qp p (V2 V1)

q=0

qp = (U2 + pV2) (U1 + pV1)

(6.6)

H = U + pV

(6.7)

q = w = pex (10 2) = 0(8) = 0

PP

qp = H2 H1 = H

qp

atm

H.U, p V

q = w = pex (8) = 1 8 = 8 L

atm
PP

10

H = U + pV (6.8)

= 16.1 L atm

H = U + pV

atm

qp

U = w
ad
PP

-p V

q = w = nRT ln

U = qV

Enthalpy (H)

qrst

q = w = 2.303 10

H = qp

158

H

H

(V = 0) U = qV,
H = U = qV

H U

P

P VA
VB P nA
nB P
P r
pVA = nART
pVB pVA = nBRT nART = (nBnA)RT
p (VB VA) = (nB nA) RT
p V = ngRT

U = H

= 37.904 kJ mol

ii

(6.9)

ng P

p V

(6.10)
H = U + ngRT
H U U H


P 100C 1 bar
P
1
41kJ mol

i 1 bar P 100C

ii

P

P r
P



P r P P
Cm
P n

P Vm
Cm
V T

pVB = nBRT

V T

159

Cp

Cp
q

V/2

qV =

CV

CV

qp =

s s

Cp

CV

H = U + (pV )

t t

= U + (RT )

= U + RT

(6.12)

s s s

H t

s s s

q = x T

t r

(6.13)

'q = C T

t
r

t t

(Calorimetry)

Cm

t
t

t


t

qV

ii

qp

t t

q q s s

(6.11)

(Bomb calorimeter)

(Sample)

160

r
V = 0

qV

g r
atm K

C r P + O2 (g) CO2 (g)

H
P

r
H = qp P
qp
rH

qp
r rH r
r qp
rH r

K K
kJ/
K atm
K rq
s
t q
CV

q = CV T

t r
r P
r r
r

161

U = -20.7 kJK

U = 2.48 10 kJ mol

ai

bi

(6.14)

CO2 (g) + 2H2O (l)

= [Hm (CO2 ,g) + 2Hm (H2O, l)] [Hm (CH4 , g) +

2Hm (O2, g)]
Hm

fus

fus

vap

Tf

CH4 (g) + 2O2 (g)

Superscript

rst q

bar

H =
r

bar

K bar

= 2.48 10 kJ mol
ng = 0

Tb

Tb

vap

162

Substance

Tf/K

fusH /(kJ

mol1)

Tb/K

vapH0/(kJ

63.15

0.72

77.35

5.59

NH3

195.40

5.65

239.73

23.35

HCl

159.0

1.992

188.0

16.15

CO

68.0

6.836

82.0

6.04

CH3COCH3

177.8

5.72

329.4

29.1

CCl4

250.16

2.5

349.69

30.0

H 2O

273.15

6.01

373.15

40.79

NaCl

108.10

C6H6

278.65

N2

28.8
9.83

(dry ice) sub =
25.2kJ mol -1

sub = 73.0 kJ mol -1
P P P P
P PP
P P q
rs t

t t
t

t rr


t
t rs

Pool g
K

100C t t

-1
373 K =40.66 kJ mol
Vap

1665.0
353.25

mol1)

170.0
30.8

18g H2O (1)

f
P P P P P P P
P P P P P PP P
PP
P P P
PPP P P
f q
f

163

C , s

qr

rt

f
r

HBr (g)

164

r r




HBr(g)


P
q st K
f


f

CaCO3(s)



rH

q












q
r

r kJ mol-1

= 285.83 kJ mol ;
s = 824.2 kJ mol
1

(6.15)

a b

a b

= 178.3kJ mol

f H (Fe, s) = 0
f H 0 (H2, g) = 0,
0

r = 3(285.83 kJ mol

1( 824.2 kJ mol1)
= (857.5 + 824.2) kJ mol1
= 33.3 kJ mol1

Stoichiometric

165

coefficients

kJ mol-1

CO (g) t

CO2

= 16.6 kJ mol =

= ( 428.7 + 412.1) kJ mol1

1

(i)

(ii)

CO(g)

(i) (iii)

(ii)

(iii)

= 110.5 kJ mol1

rH = rH1 + rH2 + rH3 ...

(6.16)

166

rH

rH1
C

rH3
rH2

298 K 1 atm
CO2(g) H2O (1)
3267.0 kJ
CO2(g)
H2O (1)
393.5 kJ mol1 285.83 kJ
1

mol

(C4H10)
2658
kJ

q r st

st q st r s

2802.0 kJ/mol

CO2(g)

H2O (1)

iii iv 3

167

ii

(i)

(ii)

v vi

H2(g)

2H(g) ;

HH

Enthalpy)

(Bond Dissociation

HH

HH

H = 435.0 kJ mol1

qr
st r t

Cl2(g)
O2(g)

2Cl(g) ;

2O(g) ;

ClCl

O=O

H = 242 kJ mol1

H = 428 kJ mol1

(Polyatomic Molecules) :

CH4

CH4(g) C(g) + 4H(g); aH = 1665 kJ mol1

Na(s)

Na(g) ;

H = 108.4 kJ mol

bond

C-H

C-H

C-H

168

P P
P P s P P P t
P P s P P

s P
P

CH4 C-H


= 416 kJ mol1

C-H P
P 416 KJ/mol
t CH3CH2Cl, CH3NO2 C-H
P *
P
P P P t P
P P P q r
s P P
P
K
H

435.8 414
347

Si

389
293
159

464
351
201
138

569
439
272
184
155

293
289
368
540
176

K
N=N

418

(6.17)**

P t

P s
P s s
P t
P t
P
P t s P
s P

P
318
264
209
351
490
213
213

Cl

339
259
327
226
230
213

431
330
201
205
255
360
331
251
243

I
297
238
201
213
213
209
180
151

H
C
N
O
F
Si
P
S
Cl
Br
I

C=C

611

946

837

615

C=O

741

891

1070

Br
368
276
243
197
289
272
213
218
192

kJ mol

C=N

(kJ mol1

O = O 498

*
** (fH bond)

169

So1

(Born-Haber cycle)

AB (s)

AB(s)

q P

Na+Cl

NaCl

170

NaCl(s)

q T qt q qt st s
qts s s

qt t s qr s
t


st
q = E0

tt

s
2 RT
+ 783 kJ mol1.

sol H

P
qr s qt q
qt qt s s q qt s
sts qr s t s
qts s s

NaCl(s)

q



q

(Driving Force)
r r



r








(Agency)

171

(Agency)

q
r q s t q
r

qs
s

N2(g) +

H2(g)

NH3(g) ;

H2(g) +

Cl2(g)

H2(g) +

H = 46.1 kJ mol1

HCl (g) ;

H = 92.32 kJ mol1
r

O2(g) H2O(l) ;

H = 285.8 kJ mol

t r r

()

t
t

r t

(Driving force)

N2(g) + O2(g) NO2(g);

r

H = +33.2 kJ mol1

H +128.5 kJ mol

r r q

6.10 ()

t q

(Isolated)

s q s
q

C (q
, s) + 2 S(l) CS2 (l);

s r r s

Bs

t q r r
q

s t q q

172

r A
B

r
A B


r




S
r



r

(Quantify)



t

U
H
S


P (q)
P S q
r
q
s

s
q


S q T

(6.18)

r
(Stotal) s

(6.19)

s
S = 0

173

Ssys =

q ss r

tt

298 K

(i)

(ii)

0 K 115 K

(ii)

(i)

549.4 JK mol

0 K

115 K

(iii)

NaHCO3

tt

(iv)

174

G
G = H - TS

(6.20)

ss

(subscript)

(6.21)

=

P

H
S
P
G H
TS [ TS = (K) (J/K) = J]


Stotal = Ssys + Ssurr
P
P
P

P
q

tt
tt

TStotal = T Ssys Hsys

(6.22)

Hsys

G




(i) (< 0)

(ii) (> 0)

TS H

T

T
P

(Summarise)

(i)

(ii)

175

S
r

(i)

(ii)

G=0
r

qs

G,

298 K

0 = rG + RT ln K

= RT ln K

G = 2.303 RT log K
r

(6.23)

29

Kp

G = 2.303 RT log Kp

mol

= 163000 J mol1
= 163 kJ mol1

G =
2.303 (8.314 J K1 mol1)
(298 K) (log 2.47 1029)

= 8.314 JK

(6.24)

2.4710

176

298 K

-1
13.6 kJ mol

= 2.38

K = antilog 2.38 = 2.4 10

= 1.33 atm.

G = RT ln K

qqst sst q 50 %
q

1
1
rG = (8.314 JK mol )

(333 K)
1
(2.303) (0.1239) = 763.8 kJ mol

(q ) (w)
U = q + w U
U q w
q w

(C) q = CT
W = pexV
pex = p W rev = pdV pV = nRT

w = 0 U = qv

177

r


tP tP

q s

S,

(i)

(ii)

(iii)

(iv)

(i) T = 0
(iii) q = 0

(ii) p = 0
(iv) w = 0

178

(i)
(ii)
(iii) < 0
(iv)

U X kJ mol1 H
(i)
= U 0
(ii) > U 0
(iv) = 0
(iii) < U 0

298 K 890.3 kJ
1
1
mol 393.5kJ mol 285.8 kJ mol1 CH4(g)
(i)

74.8 kJ mol1

(iii) +74.8 kJ mol1

(ii) 52.27 kJ mol1

(iv) +52.26 kJ mol1.

q


(i)
(ii)
(iii)
(iv)
701 J 394 J

NH2CN(s) U
742.7 KJ mol1 298 K 298 K

NH2CN(g) +
O (g) N2(g) + CO2(g) + H2O(l)
2
60.0 g 35C 55 C
Al 24 J mol1 K1
10.0C P 10C
fusH = 6.03 kJ mol1 0C
Cp [H2O(l)] = 75.3 J mol1 K1

PP
P

P
P

Cp [H2O(s)] = 36.8 J mol1 K1

CO2 393.5 kJ mol1 35.2 g CO2

CO(g), CO2 (g), N2O(g) N2O4(g) -110,-393, 81
9.7 kJ mol1 N2O4(g) + 3CO(g) N2O(g) + 3CO2(g) r

N2(g) + 3H2(g) 2NH3(g);
NH3

CH3OH(l)

O (g) CO2(g) + 2H2O(l) ; rH s = 726 kJ mol1

2
C + O2(g) CO2(g) ; cH = 393 kJ mol1
CH3OH (l) +

H2(g) +

t
O (g) H2O(l) ; f H = 286 kJ mol1.
2

179

C Cl

H (CCl4) = 30.5 kJ mol1.

vap

H (CCl4) = 135.5 kJ mol1.

H (C) = 715.0 kJ mol1 ,

H0

H (Cl2) = 242 kJ mol1

a
U = 0,
298 K

s
r

SQ

R = 8.314 JK mol
1

N2(g) +

NO(g) +

O2(g) NO(g);

O2(g) NO2(g):

H2O(l)

H = 90 kJ mol1

H = 74 kJ mol1

EQUILIBRIUM

r
r r

r r
r r r

Kp

Kc

pH

pKW

(KW)

P

P
P

t qs
s

P
s


P P
s
P



P
P
P

t

s
P
s


O2

O2

CO

CO

(System)

H2O

H 2O

(Dynamic

Equilibrium)

181

(i)

st

(Insulated)

(ii)

(i)

st

(Phase Transformation Processes)

(Operational Conditions)

(Optimize)

273 K

t
s

(iii)

(ii)

273 K

st

182

t t
r
t
t
H2O
H2O
t t
t
t r t t
r t
t
t r t
t
r
t
1 mL
t
t
t r
(i) t (ii) t (iii)
r
r t
r
t t t r
t r
t r
r
t t
(1.013 bar) 100C r
1.013 bar t 100C r

t
t 1.013
bar t
t r
t r
r
r
P

r t t

r
r
r
t
t
I2
I2
t


NH4Cl
NH4Cl
P P qs s
s

t

r t
r
t t
(Saturated)

183

(i)

(iii)

(iv)

CO2

CO2

(g)

(aq)

(aq)/ (g)

CO2 (g)

CO2 (aq)

[CO2 (aq)]/[CO2 (g)]

(i)

(Closed System)

(ii)

H2O (l)

H2O (g)

CO2

H2O (s)

qs

H2O (l)

(Non-radioactive)

(1.013 bar)

(i)

(iii)

(iv)

184

(v)

A+B C+D
(A B)
P (C D)
P



C D

A + B C + D C + D A + B

qr s t

P

r
t P

t
P
P

t q
H2
D2 (Deuterium) H2 D2
P
q q
H2 NH3 D2 ND3
H2,
N2, NH3 D2, N2, ND3

t

t P
P
(Mass Spectrometer) s
P (NH3, NH2D, NHD2
ND3)
H2, HD D2
tt

H D (Scrambling)


t (Deuterium)
tP

s
H2(g) N2(g) NH3(g)
NH3(g) P N2(g)
H2(g)

185

100 mL

5 mm

30 cm

qrs

186

H I

N2(g) + 3H2(g)
2NH3(g)

2NH3(g)

N2(g) + 3H2(g)

H2(g) + I2(g) 2HI(g)

H2 I2

H2 I2 HI

t P HI
HI
H2 I2
t P

H2(g) + I2(g) 2HI(g)

r
s





(H2, NH3 CaO)



A+BC+D
A B
C D

(Cato Maximillian Guldberg)
(Peter Waage)




(7.1)

Kc
r s
r s (Law of Mass
Action)

(Sealed Vessel) 731
K H2 I2


H2(g) + I2(g)
2HI(g)
1
1
2
t
H2 I2

187

HI

H2, I2,

HI

H2

HI

I2

H2(g) + I2(g)

2HI(g)

(Power)

'Kc'

2HI(g)

Kc ,

H2(g) + I2(g)

(Stoichiometric Coefficients)

[H2(g)]eq = [I2(g)]eq

(7.1)

'eq'

(7.2)

Kc

(7.3)

188

'c' Kc
mol L1






aA + bB cC +
cD



(7.4)

C D
A B [C],
[D]

4NH3 + 5O2 (g) 4NO(g) + 6H2O(g)

(Species)





t (Fac
tor)


(7.5)
H2(g) + I2(g) 2HI(g)

(7.6)

2HI(g) H2(g) + I2(g)

P P

P

(7.7)

(7.8)

qrsr r rsrrr rr
qrsr rsrrr rr s rr

I2(g)

H2(g) +

HI(g)

(7.9)

Kc = [HI] / [H2]1/2[I2]1/2 = x1/2 = Kc1/2

(7.10)

n
nH2(g) + nI2(g) 2nHI(g)
Kcn



rrs r

rsrrr
rr

aA+bB

c C + dD

Kc

cC+dD

aA+bB

Kc =(1/Kc )

ncC + ndD Kc = (Kcn )

na A + nb B

Kc K'c



rr
500 K N2 H2 NH3

[N2] = 1.5 10

M, [H2] = 3.0 10

[NH3] = 1.2 10 M.

N2(g) + 3H2(g) 2NH3(g)

189

800 K

N2(g) + O2(g)

'R'

(p)

'n'

bar

'V'

(L)

Kc

0.0831 bar L mol1K1

n/V

'c'

mol/L

p = cRT

p=

RT

H2(g) + I2(g)

q t

(K)

NO = 2.8 10 M

2NO(g)

N2=3.0 10 M, O2 = 4.2 10 M

= 0.106 104 = 1.06 103

pV = n RT

2HI(g)

= 0.622

s qt

N2(g) + 3H2(g) 2NH3(g)

(7.12)

qr

Fe

3+

CH3COOH (aq)
+ C2H5OH (aq)
(aq) + SCN(aq)
Fe(SCN) 2+ (aq)

qr

CH3COOC2H5 (aq) + H2O (l)

qr

qr

( Kp )

q qt

qt

2NH3(g)

(7.13)

Kp = Kc,

Kc

N2(g) + 3H2(g)

190

(7.14)

aA + bB

cC + dD

1.41 M, 1.59 M 1.59 M

PCl3 + Cl2 Kc

800 K Kc = 4.24

r
s

r sq t q

500 K PCl5, PCl3 Cl2

PCl5

CO (g) + H2O (g)

CO2 (g) + H2 (g)

800 K CO2 H2, CO H2O

(7.15)

n = [

] Kp
bar
1 bar 1
pascal, Pa = 1 Nm2 1 bar = 105Pa
Kp


Kp

CO H2O
0.1 M

CO (g) + H2O (g)

CO2 (g) + H2(g)

0.1M

0.1M

(0.1x)M

xM

xM

(0.1x)M

CO2 H2 x mol L1

2

Kc = x /(0.1 x) = 4.24
2

x = 4.24(0.01 + x 0.2x)
2

x = 0.0424 + 4.24x 0.848x

2

3.24x 0.848x + 0.0424 = 0

a = 3.24, b = 0.848, c = 0.0424

ax2 + bx + c = 0,

x = 0.848

191

x1 = (0.848 0.4118)/6.48 = 0.067

Kc

Kp

[CO] = [H2O] = 0.1 0.067 = 0.033 M

2NOCl(g)

1069 K
6

10

2NO(g) + Cl2(g)

Kc

Kp

Ca

(aq) + 2OH(aq)

2+

(0.0831 1069)

[X(s)]
'X'

mol L1

Kp Pa,
kPa, bar atm

[X(aq)]

'X'

[X(l)]

Kp = 0.033

Kc

n = (2+1) 2 = 1

Kp = 3.75 10

Kp = Kc(RT)

Ca(OH)2 (s) + (aq)

H2O(g)

H2O(l)

3.75

[CO2] = [H2-] = x = 0.067 M

0.194

4 bar
4 bar/ 1 bar = 4
(C ) 1
O

x2 = (0.848 + 0.4118)/6.48 = 0.194

bar

x = (0.848 0.4118)/ 6.48

[X(g)]

CaCO3 (s)

CaO (s) + CO2 (g)

Kp

(Dimensionless)

bar

qrs t qs

t
qrqs

H2(g) + I2(g) 2HI, Kc Kp

2NO2 (g), Kc mol/L
N O (g)

2 4

(7.16)

[CaCO3(s)] [CaO(s)]

K'c = [CO2(g)]

CO2(g)

192

CaO(s) CaCO3(s)

1100 K CaCO3(s) CaO (s)
CO2 2.0 105 Pa


P P



Ni (s) + 4 CO (g) Ni(CO)4 (g)

qrsts
2CO (g),

1000 K Kp 3.0

bar = 0 bar
CO CO2

t

CO2 x
CO2 (g) + C (s)

0.48 bar

Kp = (2x) /(0.48 x) = 3
2

4x = 3(0.48 x)
2
4x = 1.44 x
2

4x + 3x 1.44 = 0
a = 4, b = 3, c = 1.44

= [3

4(4)(1.44)]"/2 4

= (3 5.66)/ 8

Ag2O (s) + 2HNO3 (aq) 2AgNO3 (aq) + H2O (l)

CO2 (g) + C (s)

(0.48 x)bar 2x bar

2CO (g)
0

x

x = 2.66/8 = 0.33

= 2 x = 2 x 0.33 = 0.66 bar
= 0.48 x = 0.48 0.33 = 0.15 bar

193

700 K

H2

(Range)

I2

HI

Kc = 57.0

Kc

Kp

(Denominator)

Kc = 2.4 10

Kc < 10
Kc

298 K

Kc = 4.64 10

NO2

(Reaction Quotient) 'Q'

H2O

Qc

Qp

aA+bB

cC+dD

(7.19)

2HCl(g);

Qc = [C] [D] / [A] [B]

c

2HBr(g);

H2

O2

Kc = 4.1 10

Qc < Kc

(7.20)

Qc > Kc

N2(g) + O2(g)

K c = 4.8 10

31

25C

NO2

Qc = Kc

H2

N2O4

500 K

N2O4

47

300 K H2(g) + Br2(g)

18
K c = 5.4 10

300 K H2(g) + Cl2(g)

K c = 4.0 10

500 K H2 O2

K c > 10

(Numerator)

qs

Kc

10

Kc 10

I2

48

H2(g) + I2(g)

2NO(g);

2HI(g)

700 K Kc = 57.0

31

[H2]t=0.10M, [I2]t = 0.20 M

194

[HI]t = 0.40 M.
t
t

Qc

Qc = [HI]t2 / [H2]t [I2]t = (0.40)2/ (0.10)(0.20) = 8.0

Qc (8.0), Kc (57.0)
H2(g), I2(g) HI(g)
H2(g) I2(g) HI(g)
r Qc = Kc

Qc, Kc
r

Qc < Kc

Qc > Kc

Qc = Kc

2A P B + C Kc

[A] =
4
[B] = [C] = 3 10 M

Qc > Kc

qs tt

r

1 :
2 :





x

x
3 : x



4 :

5 :

13.8 N2O4 1 L

2 10

[A] = [B] = [C] = 3 10

N2O4(g) P 2NO2(g)

9.15 bar
Kc, Kp

pV = nRT
(V) = 1 L

195

= 13.8 g/92 g

x + 1.8x 5.4 = 0

= 0.15

x = [1.8 (1.8) 4(5.4)]/2

(R) = 0.083 bar L

1.8 = x / (3 x)

(N2O)4 = 92 g

x = [1.8 3.24 + 21.6]/2

= 400 K

x = [1.8 4.98]/2

pV = nRT

x = [1.8 + 4.98]/2 = 1.59

p 1

= 0.15

mol

[PCl5] = 3.0 x = 3 1.59 = 1.41 M

0.083 bar L

[PCl3] = [Cl2] = x = 1.59 M

400 K

p = 4.98 bar

N2O 4

4.98 bar

(4.98 x) bar

2x bar

9.15 = 4.98 + x

tr

Kc

r r

t r

= 2x = 2 4.17 = 8.34 bar

= 4.98 4.17 = 0.81bar

K,

x = 9.15 4.98 = 4.17 bar

qs

9.15 = (4.98 x) + 2x

2NO2

r r

r r

= (8.34) /0.81 = 85.87

Kp = Kc(RT)

380 K

1
t

3.00

PCl5

1L

Kc = 1.80

r t

G = G + RT lnQ
G

3.0
0
t PCl Pr
5

G= 0

Q = Kc

G = G + RT ln K = 0 (Kc

G = RT lnK
lnK = G / RT

x mol tr

(3-x)

PCl3 + Cl2

(7.21)

(7.22)

PCl5

tr

85.87 = Kc(0.083 400)

Kc = 2.586 = 2.6

(7.23)

x
rr r t r

Kc =

G < 0

K>1

G /RT

t rrr

196

G > 0 G/RT

, K < 1




1
G 13.8 kJ mol 298 K
Kc

G = 13.8 kJ mol1 = 13.8 103 J mol1

G = RT lnKc
3

ln Kc = 13.8 10 J/mol

8.31 J mol1 K1 298 K)

ln Kc = 5.569
5.569
Kc = e
3
Kc = 3.81 10

+ H2O +
300 K
13

Kc, 2 10

300 K G

G = RT lnKc
G = 8.314 J mol1 K1
300K

G = 7.64 104 J mol1

13

ln(2 10 )

P P PP

N2 H2


100

Kc





q





r

s
tq
s







t

s

tq

197

Qc

Kc

[H2]

[H2]

[I2]

H2(g) + I2(g)

2HI(g)

H2

I2

HI

CaCO3 CaO

CO2

Qc

Kc

Q c = Kc

H2

H2

[HI]

H2

Qc = [HI]2/ [H2][I2]

[Fe(SCN)]

H2

qs

1mL

[Fe ]/[SCN ]

3+

(7.25)

(III)

2+

(H2 C2 O4), Fe3+

198

[Fe(C2O4)3]3
Fe3+
Fe3+
[Fe(SCN)]2+ Fe3+
[Fe (SCN)]2+

HgCl2

Hg2+ SCN
[Hg (SCN)4]2
SCN [7.24]
SCN
SCN












P P
(CO + 3H2)
(CH4 + H2O)










Qc
t

[CO], [H2], [CH4] [H2O]

q r
q q
r
Qc < Kc
P P


s

(Q) (Kc)

(Kc)
H

t H

t H

199

NO2

(Dimerization)

HNO3

250mL

NO2
5mL

(araldit)

(stopper)

1, 2 3
(Freezing

1
mixture) 2
3 (363K)
2

N2O4

NO2

8 - 10

[Co(H2O)6]

3+

NO2

NH3

500C

200

NH3

NH3

NH3

st

N2O4

SO2

SO3

200

(V2O5)







P q q P q



t

100%

5%



r s

t L




Acidus

(Book binder)
(Davy)


(Royal Institute Laboratories)

(First Fullerian Professor)
(17911867)




(Disseminated)

201

HX

Cl

(<5%)

MOH

H7O

H3O+

H3O (aq)

H3O+
+

H O Cl
3

H5O , H7O
+
2

+
3

H3O+(aq)

H+(aq)

H (aq)

=1013cm

H+

Na

P P

H9O4+

H3O2 , H5O3

qq r

H9O4

202

(1859-1927)

(Thesis)


t


r

(Immuno Chemistry),
(Cosmology), (Origin In Life) (Cause Of Ice Age)






q q q






P



H+
H+

NH3 H2O

r

OH s

OH H2O OH
NH3 t r

H2O
OH NH3
s





HCl (aq), H2O
H2O

203

H3O+

H3O+, H2O

HCl, Cl

HCl

BF3

BF3

NH3

NH3

BF3 + :NH3 BF3:NH3

HF, H2SO4

HCO3

HCO3

F , HSO4

NH3

HCOO

AlCl3, Co3+, Mg2+

HO

H2O,

NH2,

NH3, OH

BCl3

H2O,

NH3, NH4

HCOOH

NH3

H3O
H2CO3
H2SO4

OH
2
CO3
2
SO 4

NH3

+
NH4

NH2

BCl3

H2O

HCO3

HSO4

HSO4

HCO3,

qrs

HCl

Cl

H3O+

tt

H2O

HCl

204

(HClO4) (HCl),
(HBr) (HI),
(HNO3) (H2SO4)


(LiOH),
(NaOH), (KOH),
(CsOH)
Ba (OH)2,
H3O OH

OH




HA

q
q
q

HA H3O+



HA, H3O+ HA
H3O+ A
H3O+

P P P

HClO4, HCl,
HBr,
HI, HNO3,
H2SO4
ClO4, Cl, Br, I, NO3 H2O

HA
(HNO2),
(HF) (CH3COOH)

NH
, O2 H
H2O
2


r s
(HIn) (In)

t

H+





s HA
s
B
s H2O
s

s
H2O(l) + H2O(l)
H3O+(aq) + OH(aq)

K = [H3O+] [OH ] / [H2O]

(7.26)

[H2O]

205

Kw

1.0 10 M
7

OH

H+

1000 g/L

OH

10 M

pH

[H3O ] < [OH ]

+

10

(<0.01M)

(H+)

pH

10
[H ]
+

pH 7

pH 7

pH = 7

14

pH

100

pH

pH

pH

[H ]
+

pH

pH

(7.29)
Kw

(Logarithmic Scale)

pH < 7

pH

pKw

pH < 7

298K

[H3O+] = [OH ]

log Kw = log {[H3O+] [OH]}

= log [H3O+] log [OH]
= log 1014
pKw = pH + pOH = 14

Kw = [H3O ] [OH ] = 10

[H3O+] > [OH ]

pH

298 K

[H3O+] = 1010 M

pH

H3O

NaOH

10 7 / (55.55) = 1.8 109 or ~ 2 in 109

pH = log (10 ) = 7

(102 M)

[OH] = 104

[H2O] = (1000 g /L)(1 mol/18.0 g) = 55.55 M.

18.0 g /mol

HCl

pH = 10

=2

pH

Kw

pH = log aH+ = log {[H+] / mol L1}

298 K Kw

Kw = [H3O+][OH ] = (1 107)2 = 1 1014 M 2

(7.28)

[OH ] = [H+] =

1.0 10 7 M

= [H+] / mol L1

(7.27)

Kw = [H ][OH ]
298 K

pH

206

pH

pH
pH 114 pH 0.5

1.0 10 M HCl pH

2H2O (l)
H3O (aq) + OH (aq)

14
Kw = [OH ][] = 10
+

pH pH

pH
pH
P pH 0.001
r rr
pH P pH
7.5


3
3.8 10 M pH

pH = log[3.8 10 ]= {log[3.8] +
3

log[10 ]}

x=[OH ]= H3O
+
H3O (i) t HCl

HCl (aq) + H2O (l) q H3O (aq)+Cl (aq)

(ii)
+
H3O
+

[H3O ] = 10
Kw = (10

+x

+ x)(x) = 1014

2
8
14
x + 10 x 10 = 0

[OH ] = x = 9.5 10

pOH = 7.02 pH = 6.98

s
r
HX
HX H+(aq)
X(aq)

HX(aq) + H2O(l) q H3O+(aq) + X (aq)
(M)
c

= {(0.58) + ( 3.0)} = { 2.42} = 2.42

pH 2.42

(M)
-c
+c

+c

pH

NaOH
0.1 M NaOH

pH
~15
13
10.5
10
7.8
7.4
6.8
6.4

lM HCl
HCl

pH
5.0
~4.2
~3.0
~2.2
~1.2
~0
~1.0

207

c-c

c=

= HX

Ka

/ c(1- ) = c

HX

/ (1- )

Ka

(7.30)

Ka

HX

Ka

pH
pH = log [H3O+]

(7.31)

Ka

HF

pH

HF

qs

(Ka)

10 4

(1) HF + H2O

4.5

10 4

(2) H2O + H2O

(HCOOH)

1.8

10 4

(C5H4NCOOH)

1.5

10 5

(HNO2)

(CH3COOH)

1.74

10 5
5

(C6H5COOH)

6.5

10

(HCIO)

3.0

10 8

(HCN)

4.9

10 10

1.3

10

pH

3.5

(HF)

H3O , F

0.22M

HF

(C6H5OH)

pKa = log (Ka)

pH

pKw

Ka

1M

Ka = [H+][X] / [HX]

Ka = c 2

pH

c
HX

(M)

10

H3O

(M)

0.02

H3O + OH
14
Kw = 1.0 10

Ka >> Kw,

H3O + F Ka = 3.2 10

HF + H2O

0
(M)

(0)

208

0.02
(M)

+0.02

0.02 0.02

+0.02

0.02

0.02

2
2
Ka = (0.02) / (0.02 0.02) = 0.02 / (1
4
) = 3.2 10

2
2
2
+ 1.6 10 1.6 10 = 0


= + 0.12 0.12
= 0.12
= 0.12
HF, F H3O+

+

[H3O ] = [F ] = c = 0.02 0.12 =

2.4

10

[HF] = c(1 ) = 0.02 (1 0.12) =

17.6

10

-3

= [HA]P/[HA] 100%

0.08 M (HOCl)
pH
2.5 10

HOCl

HOCl(aq) + H2O (l)

H3O (aq) + ClO (aq)

(M)
0.08

+x

+x

(M)
x

(M)
0.08 x
+

Ka = {[H3O ][ClO ] / [HOCl]}

2

= x / (0.08 x)
2

(7.32)

x / 0.08 = 2.5 10
2

pH = log[H ] = log(2.4 10 ) = 2.62

x = 2.0 10 , x = 1.41 10

0.1M pH 4.50
H+,A HA
Ka pKa

[H ] = 1.41 10

pH

= 10

4.50

= 3.16 10

[H ] = [A ] = 3.16 10
+

M.

= {[HOCl]P / [HOCl]}
3

100 = 1.41 10 / 0.08 = 1.76 %.

3
pH = log(1.41 10 ) = 2.85.

qr st

pH = log [H ]
[H ] = 10

Ka = [H ][A ] / [HA]
-5

[HA] = 0.1 (3.16 10 ) 0.1

5 2

Ka = (3.16 10 ) / 0.1 = 1.0 10

pKa = log(10 ) = 8

MOH

MOH(aq) M+(aq) + OH(aq)
(MOH)
M+ OH

Kb


Kb = [M+][OH] / [MOH]
(7.33)
c =

209

Kb

[OH ] = Kw / [H ] = 1 10

14

/ 1.67 10

= 5.98 10

10

298 K

Kb

5.4

(C2H5)3N

6.45

10 5

1.77

10 5

NH3 or NH4OH

10 4

1.10

10 6

C5H5N

1.77

10 9

C6H5NH2

4.27

10 10

0.2M NH4Cl

CO (NH2)2

1.3

Kb

Kb

pKb

pH 9.7

OH

(M)

+x

0.20

+x

(M)

Kb
x

0.1M

0.2 M

[OH ]= x = 0.88 10

NH2NH2 + H2O
pH

OH

0.10 x
0.20 + x
x
+

Kb= [NH4 ][OH ] / [NH3]

5
= (0.20 + x)(x) / (0.1 x) = 1.77 10

(M)

(7.34)

0.10

0.004 M

4.75

pKb = log (Kb)

NH3

NH4

Kb = 10
= 1.77 10 M
NH4+ +
NH3 + H2O

OH

pH

Kb = antilog (pKb)

NH4+(aq) + OH(aq)

NH3

NH3 + H2O

NH3(aq) + H2O(l)

t rs

0.1 M NH3

pH

pKb = 4.75

10 14

(CH3)2NH

0.004 M

Kb= [NH2NH3 ][OH ] / [NH2NH2]

5 2
7
= (5.98 10 ) / 0.004 = 8.96 10
7
pKb= logKb = log(8.96 10 ) = 6.04.

NH2NH3 + OH

[H ] = antilog (pH) =

[H ]= 1.12 10

pH = log[H ] = 8.95

10

Ka

antilog (9.7)
= 1.67 10

Kb

Ka

Kb

NH4+

210

r NH3 r
NH4+(aq) + H2O(l) H3O+(aq) + NH3(aq)
Ka = [H3O+][ NH3] / [NH4+] = 5.6 1010
NH3(aq) + H2O(l)

NH4+(aq) + OH(aq)

Kb =[ NH4+][ OH] / NH3 = 1.8 10-5

2 H2O(l)

H3O+(aq) + OH(aq)

Kw = [H3O+][ OH ] = 1.0 1014 M

Ka NH4+ r Kb, NH3

r
r
Ka r Kb r
Ka

K b = {[H3O+][ NH3] / [NH4+ ]} {[NH4+ ]

[ OH-] / [NH3]}

= [H3O ][ OH ] = Kw
+

0.05 M q r pH
r
r sts
r

NH3
r
NH3 + H2O

= (5.6 1010) (1.8 105) = 1.0 1014 M

r r


PP
K = K1 K2

(3.35)

Kb = Kw

(7.36)

Ka

r
r r r
r
pK a + pK b = pK w = 14 (298K )

r K w = K a K b
r
r

B(aq) + H2O(l) BH+(aq) + OH(aq)

Kb = [BH ][OH ] / [B]

r r r
r
r [H+]
r
Kb = [BH+][OH][H+] / [B][H+]
={[ OH][H+]}{[BH+] / [B][H+]}
= Kw / K a
Ka Kb = Kw

NH4

OH

st
r r

[OH ] = c = 0.05
2

Kb = 0.05 / (1 )

r
r r
r

r r r
r
r
r

Kb = c

or

= (1.77 10 / 0.05)

= 0.018.
4
[OH ] = c a = 0.05 0.018 = 9.4 10 M.
+

14
4
= 10
/ (9.4 10 )
[H ] = Kw / [OH ]
11
= 1.06 10
11
pH = log(1.06 10 ) = 10.97.

r
Ka Kb = Kw

r sts r NH3 Kb
+
NH4 r r
Ka = K w / K b

14

= 10
/ 1.77 10
10
= 5.64 10

r r

211

H2X

qq st

H+(aq) + HX(aq)

HX(aq)

= {[H ][HX ]} / [H2X]

(8.16)

H A

H3PO4

HA

HA

HA

298 K

H 2X

pH

(8.17)

H+(aq) + X2(aq)

= {[H+][X2-]} / [HX-]

H2X(aq)

HA

HA

HF << HCl << HBr << HI

H2CO3

H2A

H3O

H2A

H2PO4

qq

st
s

CH4 < NH3 < H2O < HF

H2A, HA

HA

HPO2
4

H2S, H2O

(Ka)

HCO3

212

CH3COOH(aq)

HAc(aq)

H+(aq) + CH3COO (aq)

H+ (aq) + Ac (aq)

H+


[H+]






0.05 M 0.05 M

pH
HAc(aq)

H (aq) + Ac (aq)

0.05

x
(M)
x

+x

+x

(M)
0.05-x

Kb = [NH4 ][OH ] / [NH3] = 1.77 10

0.05+x

Ka= [H+][Ac ]/[H Ac] = {(0.05+x)(x)}/(0.05-x)

Ka x << 0.05
(0.05 + x) (0.05 x) 0.05
1.8 105 = (x) (0.05 + x) / (0.05 x)
= x(0.05) / (0.05) = x = [H+] = 1.8 105M
pH = log(1.8 105) = 4.74

[NH4 ] = [OH ] = x
[NH3] = 0.10 x 0.10
2

x / 0.10 = 1.77 10
x = 1.33 10

= [OH ]

14
[H ] = Kw / [OH ] = 10 /

10

14

/(1.33 10 ) = 7.51 10

pH = log(7.5 10

12

12

) = 11.12

25 mL 0.1M HCl 2.5

HCl 50 mL 0.1 M
5 mL NH3 2.5
75 mL
2.5 NH3
+
2.5 NH4

NH3

HCl

2.5

(M)
0.05

NH3 + H2O NH4 + OH

Ka = [H ][Ac ] / [HAc]
+

NH4+ + Cl

2.5

2.5

2.5

75 mL 2.5 NH4+
(0.033 M) 2.5
NH3 (0.033 M)
NH3

+
NH4OH
NH4 + OH

0.033M y

+
[NH4 ]

y = [OH ] =
75 mL
+
2.5 NH4 (0.033 M)
+
NH4
+

[NH4 ] = 0.033 + y

y [NH4OH] 0.033 M [NH4+]

0.033M.

0.10 M pH

Kb = [NH4 ][OH ] / [NH4OH]

50 mL 0.10 M HCl
25.0 mL pH
K b = 1.77

= y(0.033)/(0.033) = 1.77 10

10

y = 1.77 10 = [OH ]
+

14

[H ] = 10

pH = 9.24

/ 1.77 10

= 0.56 10

213

pH

pH

Na+, K+, Ca2+, Ba2+

NO3, ClO4

Cl , Br ,

pH 7

CH3COONH4

NH4Cl

pH 7

CH3COOH

H 2O

CH3COONa
(ii)

NH4Cl,
(iii)

CH3COOH

CH3COONa(aq)

NaOH

OH

CH3COOH +
NH4OH

(pKa pKb)

(7.38)

pKb

pKa

pH = 7 +

(Ka = 1.8 105)

pH 7

pH

NH4Cl

NH4Cl(aq)

NH4OH

(aq) +Cl (aq)

=7+

[4.76 4.75]

=7+

[0.01] = 7 + 0.005 = 7.005

[pKa pKb]

HCl

pH 7

pH 7

pH = 7 +

CH3COO (aq)+H2O(l) CH3COOH(aq)+OH (aq)

OH

pH

CH3COO (aq)+ Na+(aq)

CH3COONa,

H+ + OH

NH4+ + OH

CH3COONH4

CH3COO + H+

CH3COOH

NH4OH

NH4OH

CH3COO + NH4+ + H2O

(i)

(Kb = 1.77 105)

H+

NH4OH

pH

t s

pH

pH

(Malfunctioning)

214

(Consmetic Formulation)
pH
pH

pH
pK a pK b P


pH, 4.75
P
pH, 9.25 P

q rs t

P




(Lattice Enthalpy)




P




(Overcome)


P

I
II
III

> 0.1 M

0.01 <

< 0.01 M

< 0.1 M

P


P
BaSO4(s)
Ba2+(aq) + SO42(aq),
P

K = {[Ba2+][SO42]} / [BaSO4]

P P
Ksp = K[BaSO4] = [Ba2+][SO42]

(7.39)

Ksp

Ksp
298 K 1.1 1010

P

P P
P 'S'
1.1 1010 = (S)(S) = S2 S = 1.05 105

1.05 105 mol L1

P P P
P (Zr4+)3
(PO43)4 P
4
P
'S'

[Zr4+] = 3S [PO43] = 4S

3
4
7
Ksp = (3S) (4S) = 6912 (S)
S = {Ksp / (33 44)}1/7 = (Ksp / 6912)1/7

215

298K

qst s

qs q t

'S'

MxXy(s)

xMp+(aq) + yXq (aq)

( x p+ = y q)

Ksp = [Mp+]x[Xq ]y = (xS)x(yS)y

S

(x + y)

(x + y)

Ksp

rr

23

= 1.1 10

(Dissolution)
298 K

(7.41)

Ksp= Qsp

S = (Ksp / xx . yy)1 / x + y

(7.40)

=x .y .S
= Ksp / xx . yy
x

A2X3

Qsp

Ksp

2A

3+

+ 3X

3+ 2

2 3

Ksp = [A ] [X ] = 1.1 10
S = A2X3,

3+

23

[A ] = 2S; [X ] = 3S
2

23

S = 1 10

S = 1.0 10

Ksp = (2S) (3S) = 108S

= 1.1 10

25

mol/L.

Ni (OH)2

AgCN

2.0 10

15

17

6 10

A2X3

A2X3

Ksp

216

AgCN

1
Ni (OH)2 r S mol L
Ni2+ (S) OH 2S mol L1
r OH r OH
1
(0.10 + 2S) mol L
NaOH r 0.10 mol L1 r

Ag + CN
+

17

Ksp = [Ag ][CN ] = 6 10

Ni(OH)2

Ni

2+

2+

+ 2OH

15

Ksp = [Ni ][OH ] = 2 10

[Ag+] = S1, r [CN-] = S1

15

[Ni ] = S2, r [OH ] = 2S2

2+

17

S1 = 6 10
, S1 = 7.8 10
2
15
4
(S2)(2S2) = 2 10 , S2 = 0.58 10
AgCN Ni(OH)2 r

r r r
r
r r
r r r r
Ksp = Qsp r
r r
r Ksp = Qsp
r Qsp
r r (activities)
r rr HCI
r r r
r
r r r
P
r r r
P r
r
P P

r P
r

0.10 M NaOH Ni (OH)2 r

Ni (OH)2
15

2.0 10

Ksp = 2.0 10
2
2S)

2+

= [Ni ] [OH ] = (S) (0.10 +

K sp 2S << 0.10
r (0.10 + 2S) 0.10
r 2.0 1015 = S (0.10)2
S = 2.0 10

13

2+

M = [Ni ]

r pH
r pH r

r r r
Ksp = Qsp r
r r Ksp = [M+] [X],
qs t q t s t



[X ] / [HX] = Ka / [H+]

r r

qs s q

s
r [X ] / {[X ] +
[HX]} = f = Ka / (Ka + [H+]) r
pH 'f' r pH
r S r
Ksp = [S] [f S] = S2 {Ka / (Ka + [H+])}
S = {Ksp ([H+] + Ka ) / Ka }1/2

(7.42)

r S, [H ] pH r
r
+

217

Kc

K = [C] [D] /[A] [B]

Kp

Qc

Kc

c C +d D

aA+bB

(Kb)

log[Kb r pKw = log[Kw]

pOH = pKw

(Ka)

pH

(pH = -log[H+])

(pOH = log[OH ]) ; pKa = log[Ka] ; pKb =

pH +

(Ksp)

218

P P P P
q rs t s t t t s
pH r pH tt t r
pH tt t pH r s r
tr rr t

r t r pH tt
t pH r r
q pH q t r s r
t t r
t r t t r
pH t r pH t pH tt tr t
r r

Kc [SO2]= 0.60M,

[O2] = 0.82M [SO3] = 1.90M

2SO2(g) + O2(g)

2SO3(g)

105 Pa 40%

I2 (g)

2I (g)

Kp

Kc
(i)

2NOCl (g)

(ii)

2Cu(NO3)2 (s)

(iii)

CH3COOC2H5(aq) + H2O(l)

(iv)

Fe3+ (aq) + 3OH (aq)

(v)

I2 (s) + 5F2

2NO (g) + Cl2 (g)

2CuO (s) + 4NO2 (g) + O2 (g)
CH3COOH (aq) + C2H5OH (aq)

Fe(OH)3 (s)

2IF5

Kp Kc
(i)

2NOCl (g)

2NO (g) + Cl2 (g); Kp= 1.8 102 at 500 K

(ii)

CaCO3 (s)

CaO(s) + CO2(g); Kp= 167 at 1073 K

219

NO (g) + O3 (g)

Kc

1000K Kc = 6.3 1014

N2 O2

2N2O (g)

10L 0.482 N 0.933 O

2
2
N2O Kc= 2.0 1037

500K

1.7 10

0.087 NO 0.0437 Br2

NO Br

2

2SO3 (g)

450K Kp= 2.0 1010 bar

Kp

HI(g)

20L

N2 1.57 H2 1.92 NH3 8.13

N
(g) + 3H2 (g) 2NH3 (g) Kc
2

H2O
40%

H2 (g) + CO2 (g)

700K

HI(g)

ICI,

2ICl (g)

CO 725 K 10L
CO

H2O (g) + CO (g)

Br2

H2 (g) + I2 (g)

HI(g) 0.2 atm

0.04 atm

2SO2(g) + O2(g)

2HI (g)

2NOBr (g)

0.0518 NOBr

Kc

2NO (g) + Br2 (g)

2N2 (g) + O2 (g)

NO2 (g) + O2 (g)

H2 (g) + I2 (g)

2HI (g)

700K
H2(g) I2(g)

0.78 M

I2 (g) + Cl2 (g); Kc = 0.14

899 K KP

54.8

0.5 mol L HI(g)

1

0.04 atm C2H6

220

4.0 atm C2H6

t
C2H6 (g)

C2H4 (g) + H2 (g)

t
t
CH3COOH (l) + C2H5OH (l)

CH3COOC2H5 (l) + H2O (l)

Qc
t
(ii) 293K 1.00 0.18 t
0.171 t
(iii) 0.5 1.0 293K r
0.214
437K PCl5
PCl5 0.5 101 mol L1 Kc 8.3 103
PCl3 Cl2

(i)

PCl5 (g)

PCl3 (g) + Cl2(g)

t (II)
CO2
FeO (s) + CO (g)

Fe (s) + CO2 (g); Kp = 0.265 atm at 1050K

1050K CO CO2

pCO= 1.4 atm = 0.80 atm

N2 (g) + 3H2 (g)

2NH3 (g) 500 K Kc =

0.061

3.0 mol L1 N2, 2.0 mol L1 H2 0.5 mol L1 NH3

BrCl

2BrCl (g)

Br2 (g) + Cl2 (g)

500K Kc= 32 BrCl 3.3 103 mol L1

1127K 1 atm CO CO2
90.55% CO
C (s) + CO2 (g)

2CO (g)

Kc t
298K NO O2 NO2
NO (g) +

O2 (g)

NO2 (g)

G t

221

G (NO2) = 52.0 kJ/mol

G (NO) = 87.0 kJ/mol

G (O2) = 0 kJ/mol

CaO (s) + CO2 (g)

3Fe (s) + 4H2O (g)

CaCO3 (s)

Fe3O4 (s) + 4H2 (g)

(i)

COCl2 (g)

(ii)

CH4 (g) + 2S2 (g)

(iii)

CO2 (g) + C (s)

(iv)

2H2 (g) + CO (g)

(v)

CaCO3 (s)

(vi)

4 NH3 (g) + 5O2 (g)

PCl3 (g) + Cl2 (g)

CS2 (g) + 2H2S (g)

2CO (g)

CH3OH (g)

CaO (s) + CO2 (g)

CO (g) + Cl2 (g)

4NO (g) + 6H2O(g)

1024K

1.6 105

2HBr(g)

HBr 10.0 bar

1024K

CH4 (g) + H2O (g)

PCl5 (g)

H2(g) + Br2(g)

CO (g) + 3H2 (g)

Kp

(i)

(ii)

(iii)

H2

CH3OH

CO

CH3OH

473K

CH3OH (g)

Kp

2H2(g) + CO (g)

PCl5

PCl5 (g)

Kc

PCl3 (g) + Cl2 (g)

8.3 10-3

H = 124.0 kJ mol1

222

Kc
Kc
(i) PCl5 (ii) (iii)
Kc

CO H2
CO
CO (g) + H2O (g)

CO2 (g) + H2 (g)

400 C CO
r , H2 400C Kp= 10.1

Cl2 (g)

2Cl (g) Kc = 5 1039

Cl2 (g) + 2NO (g)

2NOCl (g) Kc = 3.7 108

Cl2 (g) + 2NO2 (g)

2NO2Cl (g) Kc = 1.8

25C 3O2 (g) 2O3 (g) Kc 2.0 1050

25C O2 1.6 102 O3

CH4(g) + H2O(g) 1300K

CO 0.3 H2 0.01 H2O 0.02 CH4
Kc 3.90 CH4
CO(g) + 3H2(g)

P
2
HNO2, CN, HClO4 F , OH,
S

H2O, BF3, H+ NH4+

HF, H2SO4 HCO 3

NH2, NH3 HCOO

P H2O, HCO3, HSO4 NH3

P
OH F H+ BCl3

3.8 103 M pH

pH, 3.76

HF, HCOOH HCN 298K 6.8 104, 1.8 104

4.8 109

223

0.01M

1.0 1010 0.05M

H2S

H 2S

0.01M

1.74 105

pH

0.05 M

pH

0.003 M HCl

0.002 M HBr

pH

2 TlOH

0.3

0.3

13.6 M HCl 1mL

NaOH

0.005 M NaOH
0.002 M KOH

Ca(OH)2

(HA) pH, 4.15

pKa

0.1M HS

0.1 M HCl
1013 S2
1.2

9.1 10

500 mL

0.132 0.1M

200 mL

pH pKa

0.005M (C18H21NO3)

0.001M

7.7

5.4 104 0.02M

NaOH 0.1M

pH

pH 9.95

0.05M pKa 4.74

0.01M 0.1M HCl

6.83

7.38

pH

2.2 7.8

298K 0.561 g, KOH

298K Sr(OH)2

pH

pH

1.2

6.4

6.8, 5.0, 4.2,

200 mL

pH,

19.23 g/L

224

1.32 105 0.05M

r pH r 0.01 M HCl r
r

(HCNO) 0.1M pH, 2.34 r

r r

4.5 104 r 0.04M

pH r r

0.02M pH 3.44 r
r

r r r
NaCl, KBr, NaCN, NH4NO3, NaNO2 r KF

1.35 103 0.1M r 0.1M

pH r

310K 2.7 1014 r pH

r pH r
0.2M Ca(OH)2 10 mL + 0.1M HCl 25 mL
0.01M H2SO4 10 mL + 0.01M Ca(OH)2 10 mL

0.1M H2SO4 10 mL + 0.1M KOH 10 mL

r
7.9 r r r r r
r r
Ag2CrO4 r AgBr r 1.1 1012 r 5.0 1013
rr r r r
0.002M r r r
r t Ksp = 7.4 108

6.46 105 r Ksp 2.5 1013

3.19 pH r r t
r r r r
r r
Ksp = 6.3 1018
r r r t
Ksp = 9.1 106
0.1M HCl
r r r 1.0 1019 M
10 mL r 0.04M 5 mL r
r t FeSO4, MnCl2, ZnCl2, CdCl2.

5.7

ump.

u1,u2,u3, .un,

uav

u +u +..........u n
u av = 1 2
n

T1

T2

300 K

st

s st

s
st

qr st

qr st

st
s
s

II

1
mu 2 ,
2

u 2

u12 +u 22 +..........u 2n
n




(Root
mean square speed)

u2

u rms = u 2

urms > uav > ump

ump: uav :urms : : 1:1.128 : 1.224

6.5 r



P

P 10 mol 10 mol

aq.

HCl(g) + 10 aq. HCl.10 aq.

H = 69.01 kJ / mol

(S-1)

HCl(g) + 25 aq. HCl.25 aq.

H = 72.03 kJ / mol

(S-2)

HCl(g) + 40 aq. HCl.40 aq.

H = 72.79 kJ / mol

(S-3)

HCl(g) + aq. HCl. aq.

H = 74.85 kJ / mol

H



P

S-3 H
S-2
S-1

HCl.25 aq. + 15 aq. HCl.40 aq.

H = [ 72.79 (72.03)]
kJ / mol = 0.76 kJ / mol
H ( 0.76 kJ/mol)





6.6 r qs t

III

pH

Kb

Pr

H3O + A

[H 3O + ] [A ]
[HA]

[HA]
[H 3O + ] = Ka [A ]

Ka =

HA

HA + H2O

pH,

6.6

0K

pH = pK a log

[A ]
[HA]

[A ]
[HA]

pK a pH log

pH = pK a + log

0K

( 2)

[A ]
,
[HA]

298 K

HA]

A ]

[HA],

7.12.1.

pKa, pKb

[A ],

pH

IV

pH = pK a + log

[ ]
[ ]

-1 [A]
[HA]
pH = pKa log1



pH pK

a
pH
pKa pH
pKa 4.76

pH 4.76

pOH = pK b + log

[ r BH + ]
(-3)
[ B]

pH pH
+ pOH =14
pH + pOH = pKw pKa +
pKb = pKw (-3)

pK w pH= pK w pK a + log

[ BH + ]
[PP B]

pH = pK a + log

[ BH + ]
[ B]

(4)

q
pH


pKa pKa 9.25


9.25 pH



st
(4)

pH = 9.25 + log

[ BH + ]
[ B]

pH