&

x
x = x =

S 1 =

( x x ) = x

2
i

x v

= x t( a / 2, 1) 1/21

= a + bx

b=

xi i xi i

xi2

( x )

xi i x
2
xi2 x

(2.5)

xi 2 i xi xi i i b xi

a=
=
= bx
2

xi2 ( xi )

r=

xi i x
1/ 2
2
2
2
2

x
x

)( i )
( i

S x =

Var ( b ) =

i

2
S x 2

xi2

b t( a , 2 ) Var ( b )

Var

( )

x
i

x
x x

(2.9)

2
i

2
i

(2.7)

S x 2

(2.10 & 2.11)

1/ 2

( x x )
( x x)
2

a t( a , 2 ) Var ( a )

1/ 2

1


i = +

1/ 2

x 2 x 2
i

=b
1/ 2
2 2
i

Var ( a ) =

2
i

(2.6)

S 2 = 1 +
2 x

( x x )
x x
2

= a + bx ,

t( a , 2 ) Var ( i )

S x 2 ,

p = 68%

1, 96 S x 2 ,

p = 95%

3S x 2 ,

p = 99.7%

1/ 2

S 2
2 x

(2.13)

(2.12)

1. (Normal Distribution) Gauss

:
) ( xi ):

xi ; = xmin ; za ,

xi ; = xmin ; x za ,

(1.20)
(1.21)

) ( x ):
x ; = x min ; min ; za

1/ 2

(1.22)

, (3) = x v

2. STUDENT
:
( S 1 )
) ( x ):
S
x ; = x min ; min ; x t( , 1) 1/21

(1.26)

) ( xi ):

xi ; = xmin ; x t( , 1) S 1

(1.25)

) ( P )
S
S
x t( / 2, 1) 1/21 x + t( / 2, 1) 1/21

(1.27)

.. P = 95% P = 0.95 a = 5% a = 0.05 a / 2 = 2.5% a / 2 = 0.025

3. X 2

(! X 2 , t( , 1) Student za
Gauss).

:
) ( S 1 )
max ; a %
S 1 - .

max ; = S 1

(1.23)

X 2( , 1)

)
S 1; > S max ; a %
S 1 - .

S 1; = S max ; =

X 2(1 a , 1)

(1.24)

! a = 5% 1 a = 95% . X 2 X 2( 95, 1)
X 2( 5, 1) .

: ,
: () .
( > 240
> 120 ).

: () .
x x : .
S 1
: .
xi
: ( ).
P , a : , . % 0 100,
0 1 .. P = 95% P = 0.95

a = 5% a = 0.05

P + a = 100% P + a = 1 .. a = 0.05 P = 0.95

a = 5% P = 95% .

 pH

pX = log X

pH + pOH = 14

pKW = 14

.. HCl

pH = -log Ca

H + = Ca ,

H + =
Ca ,

pH = log

Ca

(3.11)

.. NaOH

OH = Cb ,

OH =

pH = 14 + log Cb

pOH = log Cb ,

Cb ,

pOH = log

Cb ,

pH = 14 + log

Cb

(3.12)

.. CH3COOH

pH =

H + = ( K a Ca )1/ 2

1
( pKa log Ca )
2

(3.15)

O .. 4

OH = ( KbCb )1/ 2

pOH =

1
( pKb log Cb )
2

H + =

KW

( KbCb )

1/ 2

1
1
pH = pK w pK + log C
b
2 b 2

(3.16)

.. CH3COONa

( K wC s )

1/ 2

OH = ( K hCs )1/ 2 =

K a1/ 2
pH =

( KwKa )
Kw
H + =
=
OH
Cs1/ 2

1/ 2

1
( pK w + pK a + log Cs )
2

(4.5)

.. NH4Cl

1/ 2
K wCs )
(
= ( K h Cs ) =

( Kb )1/ 2
1/ 2

pH =

1
( pK w pKb log Cs )
2

.. CH3COOH CH3COONa

C
H + = Ka a

Cs

pH = pK a log Ca + log Cs

pH = pK a = log

Cs
Ca

(4.11)


.. NH4OH NH4Cl

C
OH = K b b

Cs

K C
H + = w s
KC
b b

pOH = pKb + log

pH = pK w pKb log Cs + log Cb

Cs
Cb

.. CH3COONH4

(K K )
= w a
1/ 2

( Kb )

1/ 2

pH =

1
( pK w + pK a pKb )
2

.. aHCO3

H + = ( K1K 2 )1/ 2

pH =

1
( pK1 + pK 2 )
2

Ca

: , mol/ l

Cb

: , mol/ l

Cs

: , mol/ l

K a , K b :
K w , K h :

B +

u = KCB

K = Ae E / RT

(5.1)

u
K
CB
A
E
R
T
t
CB0

:
:
:
:
:
:
:
:
:

, mol/( l min)
, min-1
t , mol/ l
, min-1
, kcal/mol
, 1.99 x 10-3 kcal / (mol K)
,
, min
, mol/ l

ln CB / CB0 = Kt

(5.2)

q=

Q
t

dQ
d
= K S
dt
d

(16.1)

: , kcal
: , s

q
K
S

:
:
:
:
:

, kcal/s
, kcal / ( s m2 (oC /m) )
, m2
, oC
, m

i

i i
q K

= q =
S
/K

(16.2)

: , m
: , kcal / (m2 s)
: , C

?1
1

K1
K1

K?
?2
2

K
l1
1

K2

?3
3

l?

?4
4

l2
2

q
= 1 2 = 2 3 = 3 4 = 1 4
q =
1

2
1
S
K
K1
K2
K

i i

(16.6)


1
1
1
1

=
+
+
= 1 + + 2
K
K
K
K
K1 K K 2
1
2

1
2
dQ
= q = K (1 4 )
S dt
1 , 2 , 3 , 4

1 , 2

K1 , K 2 , K
K

(16.7)

(16.9)

, C
, m
, m
1 (), 2 (),
, kcal / ( s m2 (oC /m) )
: , kcal / ( s m2 oC )

:
:
:
:

( K )

:
l
1
1
1
1
l
l
=
+
+
= 1 + + 2
K1 K K 2
K
K1 K K 2
l1
l2
l

(16.7)

:
1
K 1

d
1
1
1

d
+
+
= 1 + 1 + 2 1
K1
K d M
K 2 d 2 K1 K d M K 2 d 2
1
2 d1
d1

K1 , K 2 , K

1 , 2

d1 , d 2
dM

K 1

(16.10)

: 1, 2
, kcal / ( s m2 (oC /m) )
: 1 2, m
: , m
: ,
, 1 2, m
d +d
: , d M = 1 2
2
d d
, d M = 1 2
ln ( d1 / d 2 )
: ,
1, kcal / ( s m2 oC )
7


1. :

2 = f (1 )

(16.11)

m1C p1 (1s 1 ) + m2C p 2 ( 2 s 2 ) = 0

(16.12)

m1 , m2

: 1 2, , kg

C p1 , C p 2

: 1 2, kcal / (kg oC)

1s , 2 s
1 , 2

: 1 2 t = 0 , oC
: 1 2 t , oC

2.
1 1s 1 f :

t =

1s
1 f

m1 C p1
S1 K 1

1 f

d1
1 2

1s

(16.15)

: 1 , oC
: 1 , oC

S1

K 1

:
.
1, m2
: ,
1, kcal / ( s m2 oC )

(16.30).

2 = f (1 )

1. :

(16.16)

:
i

m1 C p1 (1, 1, ) + m2 C p 2 ( 2, 2, ) = 0

(16.17)

m1 , m2
C p1 , C p 2

: 1 2, , kg/s

1, , 1,

: 1 ,
,
. ,
1 .

: 1 2, kcal / (kg oC)

 2, , 2, : 1 ,
,
. ,
2 .

! (16.17)
, .
2. ( ) :
i

1,

m1 m1 C p1
S F 1 ST 1 1 K 1

1,

d1
1 2

(16)

m1

: 1, kg/s

m1

: 1 , kg/m

SF1

: 1, m2

ST 1
C p1

: 1,
, m2/m
: 1, kcal / (kg oC)

: 1, kg/m3

K 1 : ,
1, kcal / ( s m2 oC )
(16) (), :
i

d1

1,

m1 C p1

d1 K 1

1,

d1
1 2

(16.29)

: ,
, 1, m

(16.15) (16.29)
:
x2

dx

ax +

x
1

1 ax2 +
.
ln
a ax1 +

(16.30)

ppm (mg / l)
N 2V 2 100
1000
V1
2

mg CaCO3 / l

(oF)
N 2V 2 100
100 mg CaCO3 /100 ml
V1
2

(D)
2V 2 56
100
V1
2

V1

mg CaO / 100 ml

: , 100ml

N 2 : HCl D
V2 : HCl D ml,

1 D = 10 ppm CaO = 17.9 ppm CaCO3
1 oF = 10 ppm CaCO3 = 5.6 ppm CaO
1 oD = 1.79 oF

07

7 15

F :
F : ()

15 32 oF :
32 55 oF :
> 55

F :

10

20.000 S/cm,
:
y = 3.5418 x 0.921
:

y S/cm
x ppm

ppm x:
x = 10(

log y log 3.5418 ) / 0.921

ppm mol/m3 58.5 ( NaCl).

J p = A ( P )
J p :
A :
P :
:

(15.1)

()
, m3 / s
, m3 /s a
, Pa

( ), Pa,
=

(atm) NaCl :
= 2CRT

(15.3)

C : , mol/l
R : , R = 0.082 l atm/(mol K)
T : , K

atm a 1.01325 x105.

, 1 bar = 1 x 105 Pa.

11

 :
J s = B C s

(15.2)

J s : , mol/s
B
: , m3/s
Cs :
, mol/m3,
Cs = CF C p
CF , , mol/m3
C p , , mol/m3
% , % Rr , :

% Rr = 1 C p / CF 100

(15.4)

CF : , mol/m3
C p : , mol/m3
%
, % a ,
:

% a = J p / J F 100
J p :
JF :

(15.5)

()
, m3/s
(), m3/s

, :
J F = J p + Jb

(15.6)

:
J F CF = J pC p + J bCb

J b : (,
), m3/s
Cb : , mol/m3
12

(15.7)

a=

(Normal Distribution)

0.000
0.126
0.253
0.385
0.524
0.674
0.842

z a

.
za
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
1.40
1.45
1.50

A
1 A 2

1 A

za

0.399

0.0000

1.0000

0.398

0.0399

0.9601

0.397

0.0797

0.9203

1.50
1.55
1.60
1.65
1.70
1.75
1.80
1.85
1.90
1.95
2.00
2.05
2.10
2.15
2.20
2.25
2.30
2.35
2.40
2.45
2.50
2.55
2.60
2.65
2.70
2.75
2.80
2.85
2.90
2.95
3.00
4.00
5.00

1.50
1.55
1.60
1.65
1.70
1.75
1.80
1.85
1.90
1.95
2.00
2.05
2.10
2.15
2.20
2.25
2.30
2.35
2.40
2.45
2.50
2.55
2.60
2.65
2.70
2.75
2.80
2.85
2.90
2.95
3.00
4.00
5.00

1.036
1.282
1.645
1.960
2.576
3.291
3.891
13

1.036
1.282
1.645
1.960
2.576
3.291
3.891

0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
0.45
0.50
0.55
0.60
0.65
0.70
0.75
0.80
0.85
0.90
0.95
1.00
1.05
1.10
1.15
1.20
1.25
1.30
1.35
1.40
1.45
1.50

0.126
0.253
0.385
0.524
0.674
0.842

0.394
0.391

0.1192
0.1585

0.8808
0.8415

0.387

0.1974

0.8026

0.381

0.2358

0.7642

0.375

0.2737

0.7263

0.368

0.3108

0.6892

0.361

0.3473

0.6527

0.352

0.3829

0.6171

0.343
0.333

0.4177
0.4515

0.5823
0.5485

0.323

0.4843

0.5157

0.312

0.5161

0.4839

0.301

0.5467

0.4533

0.290

0.5763

0.4237

0.278

0.6047

0.3953

0.266

0.6319

0.3681

0.254
0.242

0.6579
0.6827

0.3421
0.3173

0.230

0.7063

0.2937

0.218

0.7287

0.2713

0.206

0.7499

0.2501

0.194

0.7699

0.2301

0.183

0.7887

0.2113

0.171

0.8064

0.1936

0.160
0.150

0.8230
0.8385

0.1770
0.1615

0.139

0.8529

0.1471

0.130

0.8664

0.1336

0.3989

0.0000

1.0000

0.3958

0.1000

0.9000

0.3863
0.3704

0.2000
0.3000

0.8000
0.7000

0.3477

0.4000

0.6000

0.3178

0.5000

0.5000

0.2800

0.6000

0.4000

za

za
Y

1 A

0.1295

0.8664

0.1336

0.1200

0.8789

0.1211

0.1109

0.8904

0.1096

0.1023

0.9011

0.0989

0.0940

0.9109

0.0891

0.0863

0.9199

0.0801

0.0790

0.9281

0.0719

0.0721

0.9357

0.0643

0.0656

0.9426

0.0574

0.0596

0.9488

0.0512

0.0540

0.9545

0.0455

0.0488

0.9596

0.0404

0.0440

0.9643

0.0357

0.0396

0.9684

0.0316

0.0355

0.9722

0.0278

0.0317

0.9756

0.0244

0.0283

0.9786

0.0214

0.0252

0.9812

0.0188

0.0224

0.9836

0.0164

0.0198

0.9857

0.0143

0.0175

0.9876

0.0124

0.0154

0.9892

0.0108

0.0136

0.9907

0.0093

0.0119

0.9920

0.0080

0.0104

0.9931

0.0069

0.0091

0.9940

0.0060

0.0079

0.9949

0.0051

0.0069

0.9956

0.0044

0.0060

0.9963

0.0037

0.0051

0.9968

0.0032

0.0044

0.9973

0.0027

0.0001

0.99994

0.00006

0.000001

0.9999994

0.0000006

0.2331

0.7000

0.3000

0.1755

0.8000

0.2000

0.1031

0.9000

0.1000

0.0584

0.9500

0.0500

0.0145

0.9900

0.0100

0.0018

0.9990

0.0010

0.0002

0.9999

0.0001

 STUDENT
.

/2

df

40% 0.4

30% 0.3

20% 0.2

10% 0.1

5% 0.05

2.5% 0.025

1% 0.01

0.5 % 0.005

1
2
3
4
5

0.325
0.289
0.277
0.271
0.267

0.727
0.617
0.584
0.569
0.559

1.376
1.061
0.978
0.941
0.920

3.078
1.886
1.638
1.533
1.476

6.314
2.920
2.353
2.132
2.015

12.706
4.303
3.182
2.776
2.571

31.826
6.965
4.541
3.747
3.365

63.657
9.925
5.841
4.604
4.032

6
7
8
9
10

0.265
0.263
0.262
0.261
0.260

0.553
0.549
0.546
0.543
0.542

0.906
0.896
0.889
0.883
0.879

1.440
1.415
1.397
1.383
1.372

1.943
1.895
1.860
1.833
1.812

2.447
2.365
2.306
2.262
2.228

3.143
2.998
2.896
2.821
2.764

3.707
3.499
3.355
3.250
3.169

11
12
13
14
15

0.260
0.259
0.259
0.258
0.258

0.540
0.539
0.538
0.537
0.536

0.876
0.873
0.870
0.868
0.866

1.363
1.356
1.350
1.345
1.341

1.796
1.782
1.771
1.761
1.753

2.201
2.179
2.160
2.145
2.131

2.718
2.681
2.650
2.624
2.602

3.106
3.055
3.012
2.977
2.947

16
17
18
19
20

0.258
0.257
0.257
0.257
0.257

0.535
0.534
0.534
0.533
0.533

0.865
0.863
0.862
0.861
0.860

1.337
1.333
1.330
1.328
1.325

1.746
1.740
1.734
1.729
1.725

2.120
2.110
2.101
2.093
2.086

2.583
2.567
2.552
2.539
2.528

2.921
2.898
2.878
2.861
2.845

21
22
23
24
25

0.257
0.256
0.256
0.256
0.256

0.532
0.532
0.532
0.531
0.531

0.859
0.858
0.858
0.857
0.856

1.323
1.321
1.319
1.318
1.316

1.721
1.717
1.714
1.711
1.708

2.080
2.074
2.069
2.064
2.060

2.518
2.508
2.500
2.492
2.485

2.831
2.819
2.807
2.797
2.787

26
27
28
29
30

0.256
0.256
0.256
0.256
0.256

0.531
0.531
0.530
0.530
0.530

0.856
0.855
0.855
0.854
0.854

1.315
1.314
1.313
1.311
1.310

1.706
1.703
1.701
1.699
1.697

2.056
2.052
2.048
2.045
2.042

2.479
2.473
2.467
2.462
2.457

2.779
2.771
2.763
2.756
2.750

40
60
120

0.255
0.254
0.254
0.253

0.529
0.527
0.526
0.524

0.851
0.848
0.845
0.842

1.303
1.296
1.289
1.282

1.684
1.671
1.658
1.645

2.021
2.000
1.980
1.960

2.423
2.390
2.358
2.326

2.704
2.660
2.617
2.576

14

 X 2
.

, (%)

df

0.5

2.5

10

90

95

97.5

99

99.5

1
2
3
4
5

0.000039
0.0100
0.0717
0.207
0.412

0.00016
0.0201
0.115
0.297
0.554

0.00098
0.0506
0.216
0.484
0.831

0.0039
0.1026
0.352
0.711
1.15

0.0158
0.2107
0.584
1.064
1.61

2.71
4.61
6.25
7.78
9.24

3.84
5.99
7.81
9.49
11.07

5.02
7.38
9.35
11.14
12.83

6.63
9.21
11.34
13.28
15.09

7.88
10.60
12.84
14.86
16.75

6
7
8
9
10

0.676
0.989
1.34
1.73
2.16

0.872
1.24
1.65
2.09
2.56

1.24
1.69
2.18
2.70
3.25

1.64
2.17
2.73
3.33
3.94

2.20
2.83
3.49
4.17
4.87

10.64
12.02
13.36
14.68
15.99

12.59
14.07
15.51
16.92
18.31

14.45
16.01
17.53
19.02
20.48

16.81
18.48
20.09
21.67
23.21

18.55
20.28
21.96
23.59
25.19

11
12
13
14
15

2.60
3.07
3.57
4.07
4.60

3.05
3.57
4.11
4.66
5.23

3.82
4.40
5.01
5.63
6.26

4.57
5.23
5.89
6.57
7.26

5.58
6.30
7.04
7.79
8.55

17.28
18.55
19.81
21.06
22.31

19.68
21.03
22.36
23.68
25.00

21.92
23.34
24.74
26.12
27.49

24.73
26.22
27.69
29.14
30.58

26.76
28.30
29.82
31.32
32.80

16
18
20
24
30

5.14
6.26
7.43
9.89
13.79

5.81
7.01
8.26
10.86
14.95

6.91
8.23
9.59
12.40
16.79

7.96
9.39
10.85
13.85
18.49

9.31
10.86
12.44
15.66
20.60

23.54
25.99
28.41
33.20
40.26

26.30
28.87
31.41
36.42
43.77

28.85
31.53
34.17
39.36
46.98

32.00
34.81
37.57
42.98
50.89

34.27
37.16
40.00
45.56
53.67

40
60
120

20.71
35.53
83.85

22.16
37.48
86.92

24.43
40.48
91.58

26.51
43.19
95.70

29.05
46.46
100.62

51.81
74.40
140.23

55.76
79.08
146.57

59.34
83.30
152.21

63.69
88.38
158.95

66.77
91.95
163.64

X a2

2
2
= n 1 + za
,
n
n
9
9

za n .
2
= 60 1 0.00370 + 2.326 ( 0.06086 ) = 60 (1.1379 ) = 88.4 99 % n = 60 .
, X 0.99
3

15

 V. 25 C.

K1 = 7.52 x 10-3

,
CH3COOH

1.76 x 10-5

, H3PO4

K 2 = 6.23 x 10-8
K 3 = 5 x 10-13
K1 = 5.0 x 10-3

, COOH

1.77 x 10-4

, H3AsO4

K 2 = 4.0 x 10-5
K 3 = 6.0 x 10-10

, HF

2- 1,2,3 , C6H8O7

6.9 x 10-4

, HCN
, 2

7.24 x 10-10
4.5 x 10-4

, H3BO3

5.8 x 10-10

, ClCH2COOH
, CNCH2COOH
, C6H5CH2COOH
, C6H5COOH
o- , ClC6H4COOH
- ,
C6H4(NO2)COOH

K1 = 9.20 x 10-4
K 2 = 2.69 x 10-5
K 3 = 1.34 x 10-6

1.5 x 10-3
3.49 x 10-3
4.88 x 10-5
6.37 x 10-5
1.20 x 10-3

(), 4OH
, CH3NH2
, (CH3)2NH
, N(CH3)3
, CH3CH2NH2
, (CH3CH2)2NH

4.38 x 10-4
5.20 x 10-5
5.45 x 10-5
5.6 x 10-4
1.2 x 10-3

6.00 x 10-4

, (CH3CH2)3

6.4 x 10-4

, CH3CH2COOH

1.34 x 10-5

4.0 x 10-10

, C6H5OH

1.3 x 10-10

, C6H5NH2
, C5H5N
, C9H7N
, (CH2)5NH

, H2S

, H2SO3
, H2SO4
, H2CO3
,
(COOH)2
, CH2(COOH)2

, CH2CH2(COOH)2
d- 2,3-- ,
CH2(OH)CH2(OH)(COOH)2

K1 = 9.1 x 10-8
K 2 = 1.2 x 10-15
K1 = 1.7 x 10-2
K 2 = 1.0 x 10-7
K 2 = 1.15 x 10-2
K1 = 4.31 x 10-7
K 2 = 5.61 x 10-11
K1 = 5.9 x 10-2
K 2 = 6.4 x 10-5
K1 = 5.9 x 10-3
K 2 = 6.4 x 10-6
K1 = 6.63 x 10-5
K 2 = 2.54 x 10-6
K1 = 1.04 x 10-3
K 2 = 4.55 x 10-4
16

1.79 x 10-5

2.0 x 10-9
6.0 x 10-10
1.3 x 10-3

 V. K w .
(oC)
0
5
10
15
20
25
30
35
40
45
50
55
60

K w x 1014
0.12
0.19
0.29
0.45
0.68
1.01
1.47
2.09
2.92
4.02
5.47
7.30
9.61

VI. pH.

17

 VII.

20 C

100 C

20 C
100 C
20
100 C

100 C
n- 20 C
CO2 20 C

,
K ( kcal / m s oC)

,
( kg / m3 )

,
C p ( kcal / oC kg )

,
n ( decapoise) *

0.6 x 10-5

1.205

0.24

18.2 x 10-6

0.75 x 10-5

0.95

0.24

21.8 x 10-6

14.2 x 10-5
16.1 x 10-5

998
958

0.999
1.007

3.6 4.2 x 10-5

950-880

0.60 0.45

1.02 x 10-3
0.288 x 10-3
50 200 x 10-3 (20 C)
5 20 x 10-3 (100 C)

0.60 x 10-5

0.597

0.51

12.5 x 10-6

3.2 x 10-5

660

0.60

0.326 x 10-3

0.36 x 10-5

2.1

0.20

14.8 x 10-6

* 1 decapoise = 101 poise 1 poise = 10-1 decapoise

1 centipoise = 10-2 poise 1 poise = 102 centipoise
, 1 decapoise = 103 centipoise
20 C 1.02 x 10-3 decapoise = 1.02 centipoise

18