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كيمياء الديناميكا الحرارية. د/ هناء ابو المجد. الديناميكا الحرارية Thermodynamics. تعاريف ومصطلحات الديناميكا الحرارية :. 1ـ الديناميكا الحرارية : هي فرع من فروع الكيمياء القديمة التى تبحث عن العلاقة بين الحرارة والشغل ، وتحويل إحداهما إلى الأخرى .

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6136185

/


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Thermodynamics

:

1 : .

.

.

:

.


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-

- :

-

-

-

- ( ) ( )


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( ) ,

  • 2 Thermodynamics system :

surrounding : .

: 1 . 2 . 3 4 ( (

5 6 7


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:

open system: .

closed system: .

isolated system:

( ). .


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Description of the system:

:

( )

( )

properties of a system : :

1- : -

2- : .

internal energy ( .


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:

1- Thermodynamic equilibrium : .

:

2- Dynamic equilibrium :

3- Chemical equilibrium :


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work:

( ) .

99-100

:

.


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Heat:

( ) .

.

:

( ) ( )

E ( ).

: 1- ( ) ( )

2- () ()


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:

101 107

( ) : ( 1 ) . ( 2 ) . q W

q = W + D E

D E = q - W


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E

(

...)

.

( )

.

.

( )

.

( .)

( )


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( ) :

- Isobaric process : ( ) ( ) . .( ( 2- Isochoric process isovolumetric process : ( ) ( ) . 3- Isothermal process : ( ) ( ( 4- Adiabatic process : .


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( ) :

-1 : V=

( (

: W= ( (

W = 0

2 : ( ) .

W=

W = P DV = P (V2 V1)


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3- :

. : W = P1V1 log (V2 / V1)

: P1 V1 = P2 V2 ( V2/ V1) = ( P1 /P2) :

W = P1V1 log (P1 / P2)

E = 0 = q - W

W = q

4- ) )

:

W = - DE


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:


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-

  • .

  • .

    2 H Cl H H +ClCl

  • ( ).

  • = .

  • .

  • H = .

  • . ( )

  • (+)

  • (-)

  • :- .

  • :- .


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  • :

  • :

DH = H - H

  • : H H DH

  • : H H DH


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H = .

= 675 + (-860) =-185 kJ

H2 + Cl2 2HCl, H= - 185 K j

DH . :-

H2 = 435 kJ , Cl2 = 240 kJ, HCl = 430 kJ

=

DH : CH4 + Cl2 H3Cl + HCl

. :

CH3 H = 104 kcal, Cl-Cl = 58 kcal, H-Cl = 103 kcal, CH3-Cl = 84 kcal


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  • CH4 C-H !!

    CH4 CH3 + H DH = +425 KJ/mol

    CH3 CH2 + H DH = +470 KJ/mol

    CH2 CH + H DH = +416 KJ/mol

    CH C + H DH = +335 KJ/mol

  • C-H C-H

  • (1646 / 4 = 412 KJ C-H). :

    CH4 C + 4H, DH = +412 KJ/mol


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1- : ( ) .

:

I-I Br-Br Cl-Cl F-F

(nm) 0.226 0.228 0.199 0.142

(KJ) +151 +193 +242 +158

2- : .

:

C-O CC C=C C-C C=O

(KJ) +858 +837 +610 +346 +745

3- :

:

N-H O-H F-H

0.9 1.4 1.9

(KJ) +388 +463 +562


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( )

: 1 ( q2) ( ((T2) 2 ( ( 3 ( q1) ( T1).

DE = q W = (q2 q1) W

E = (q2 q1) W = 0

W = (q2 q1)


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-

1 ( (

2 .

3 ( ) .

4 .


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/

( 1796 1832). . :

1- q . Th ( )

2- ( ) .

3- ( )

4- ( ) .


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/

PV = nRT P = (nRT) / V

W = PdV= (nRT / V) dV = nRT (dV)lV

= nRTln (V2 l V1 )

1- q = W = n RThln (VB/VA) W = + q = +

2- W = n RThln (VC/VB) W = + q = 0

3- q = W = nRTcln (VD/VC) W = - q = -

4- W = nRTcln (VA/VD) W = - q = 0


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/

: : ( ) . : .

: 1 .

2 .

  • = / = 2W / q

  • W = q2 q1 = (q2-q1) / q2 = ( 1- (q2/q1

  • = ( 1- (Th/Tc

  • 1: 5 KJ 2 kJ

  • ()

  • 2: (%30) 700 J


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:

" ( ) ( )".

  • - ".

  • .

    1- :

    .

    .

    .

    .

    .


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:

(c ) (CO2) CO2 . C + O2 CO2

. H2 + O2 H2O

NaOH H2 Na 2Na + 2H2O2NaOH + H2

.

AgCl NaCl AgNO3 . NaCl + AgNO3NaNO3 + AgCl

- .

- .


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  • ( ).

  • :

    CH4 (g) + 2O2 (g)CO2 (g) + 2H2O(L) H = - 890 kJ

    O(g) + O2 (g) O3 (g) H = - 107.2 kJ

    .

    - .

    - . :

    (NH4Cl) !!

    NH4Cl(s)NH+4(aq) + Cl- (aq) H = + 14.0 kJ

(DH) (DH )


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() S

( ) ( ) . :

( ).

:

.

- ( ) .

  • ( ) .

    ( NH4Cl ) .

    .


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() S

  • ((DS > 0

  • ( .

- (q) T :

J/K) )


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  • : :

  • 1 .

  • 2 .

  • .

  • :

D E = q - W

1- ( ): . .

2- ( ): .

- .

3- ( ) :


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/

  • .

  • (St ) Ss )) (Sr ) St = Ss + Sr

  • St > 0 . St = 0

( ) DG : G = H - TS

:

: S = H / T

0 = H TS , TS = H

1 :

1 100 oC


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  • : (0 K)

  • (S)

  • .

  • : 0 K 298 K


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:

-

- .

  • .

  • : .


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:

(So)p: :(So)R

1: :

:

1: :

1: :


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DG0 . : G0 = H0 - TS0

S0 = nPSoP - nRSoR

H0 = nPHoP - nRHoR

G0 = nPGoP - nRGoR

P R n

  • DG (DG0 > 0)

  • DG (DG0 < 0)

  • DG H S

  • DG H S


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G = Go + RT lnQ

  • : R .(8.314 J/mol K)

  • : Q

  • DG DGo = - RT lnKeq Keq

  • -

  • DGo ln K K ( ) .

  • DGo ln K K ( ) .

  • DGo = ln K = K = 1 = .


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1:

N2(g) + O2(g)2NO(g) K = 1.7 x 10-2

2:

H2(g) + I2(g)2HI(g)K = 1.5

( )

3. 25 G = - 103.72 kJ

CCl4(L) + H2(g)HCl(g) + CHCl3(L)

2 K= 5.04 x1017 25

C2H4(L) + H2(g)C2H6(g)

G ( )


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: ( . Engine. Engine . . ( ) . : . .


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: : .

: .

: 1 : ( ) 2 : ( ) . : .


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:

1 ( ) ( ) ( ) 2 ( ) ( ) ( )3 ( ) ( ) ( )4 ( ) ( )


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:

= / ( )

: ( )

( ) :

= -

() = ( / ) = / ( - )

* : ( )

( )

:

= -

() = / = / ( - )

: 1 .


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