Χ. ΚΡΟΥΠΗΣ Χημική Θερμοδυναμική (E-class)

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, MSc, PhD

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Principles of Chemistry: a Molecular Approach by N.J. Tro 6, 14 ( 14.8) 17

Lehningers Principles of Biochemistry by D.L. Nelson and Michael Cox

1.3 13.1 13.2 (. 641-665)

[ . ,

. . ] 4 ( 4.16)

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Textbook of Biochemistry with Clinical Correlations by T.M. Devlin (. 14.2) Basic Medical Biochemistry: a clinical approach by D.B. Marks, A.D. Marks and C.M. Smith Biochemistry by J.B. Berg, J.L. Tymoczko and L. Stryer Principles of Biochemistry by G.L. Zubay, W.W. Parson and D.E. Vance Color atlas of Biochemistry by J. Koolman, K.H. Roehm (. 16-21 122-125) Biochemistry by R.H. Garrett and C.M. Grisham Principles of Modern Chemistry by D.W. Oxtoby and N.H. Nachtrieb Biochemical calculations by I.H. Segel .. .

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- - - - Gibbs - - /

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: .. :

2H2O O2 + 2H2 C + 2H2O CO2 + 2H2

? ? ? ? ? : !

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(system boundaries) (surroundings)

(open) + + (closed) - + - - (isolated-adiabatic)

#2

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(state functions): .. , , , 1) = ( ) 2) ?

(Intensive) p, T

NAI (extensive) E, H, S

() (Internal energy, U)

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: = -

E = +

E =

= += 0

() q>0 () q

-

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P h2 h1

V2 V1 V=V2-V1

P (P = 0) w = F h = P A h = P V

(.. , V +) w0

w = - P V

:

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: , ( .. , ) : = 0 : = q + w ( + = 0) ( )

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V=0, w = 0 = qv

: (calorimeter) q = m cs (cs specific heat capacity) : 1 cal (= 4,18 J) 1 g 14,5 C 15,5 C

= q + w

q = -q = -q v = -

q = C

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P , P = 0, : = qp + w = qp + (- P V) = qp - P V = + P V = qp - P V + P V = qp

: = + PV (-) = + (, V)

! P, V .

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/, : =

C(s) + 2H2(g) CH4(g), = -74,7 kJmol-1

, + , T, P

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= (PV) P V = n R T = (nRT) = - R T n

n = n n : n, n>0, > n, n

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1,8 g H2O 4,1 kJ (100 C) 1 atm 2(l) H2O(g) = ? = ?

1,8 g = 0,1 mol 4,1 kJ 1 mol 41 kJ = qp = = (PV) = (nRT) = - R T n = = 41 8,3143731/1000 = 41 3,1 = 37,9 kJmol-1

(1000 J = 1 kJ)

Hess

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,

: 2(g) + O2(g) NO2(g) = +33,1 kJ

, ,

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: : 1 atm ( ) /: 1 atm :

25C = 298 K , C = 1 M

= ( ) :

(formation), H: 1 mole

H = 0 kJ/mol () 1

CO

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C O: C + O CO(g)

:

C, H = 0 :

C(s, ) + O2(g) CO(g)

1: C(s, ) + O2(g) CO(g)

25C = 298 K

: -110,5 kJ/mole

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( )

H = npH() - nrH()

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? : (.. , Fe, NaCl, ) - -: S = S- S

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S = kB ln W kB = R / n Avogadro = 8,314/6,023 1023 J-1 = Boltzmann W =

( )

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S > S > S ST2 > ST1, 2>1

:

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[ ] (S>0) S 0, S= 0, () S

S

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H2 O2 (H2O)

S= -Q/T= - / ( P)

S = S + S

:

S> - S , S > 0

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+

()

C6H12O6 + 6O2 6CO2 + 6H2O

#2

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.. -, -, -DNA, , - : : () !

+ van der Waals

! S=0

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There is a tide in the affairs of men, Which, taken at the flood, leads on to fortune; Omitted, all the voyage of their life Is bound in shallows and in miseries. ()

125 (negative entropy = negentropy) , ,

:

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, (W 0) , : JM-1K-1 kJ M-1K-1! So (25 C, 1 atm) [So 0] : - - - -

C(s, ) 2,4 C(s, ) 5,7

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231 (kcalM-1K-1): -: 36,04 -: 23,38 -: 1,05 -: 0,01 : 60,47

S0

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: S0 = npS0 nrS0 .. H2O(l) H2O(g), S0 =?

S0 = 188,7 70 = +110,7 JK-1

Gibbs

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G = H TS G = - S ( P, T)

G S

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S 0: G < 0 () G > 0 - () ( ) G = 0 ()

S = S + S = S / - S = - S + = - S = G

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S G

+ + +

-

+ - +

- + -

- - +

-

G = - S

Ia. Ib. II. III. IVa. IVb.

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C() C() = 0 () - 0 () = (+1,9) (0) = 1,9 kJ mol-1 >0 S = S0() S0() = (2,38) (5,74) = - 3,36 Jmol-1K-1 0 ( 25 C) !

C() C() ( ) !!

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25 C 1 atm

IV.

NaCl

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25 C 1 atm

.

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H2O(l) H2O(s), = -6 kJ < 0, S= -22 JK-1

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G0 = npG0. nrG0.

G0 P = 1 atm, C = 1 M, T = 298 K

G0 = 0. S0

, G0 0 S

G0 = 0

G0 >0:

(.. , )

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+ +

Kc: Kc = k1/k2 = [] [] / [] [] k1, k2

, P V = n R T P = n/VRT P = C R T C = P/RT Kp = [P] [P] / [P] [P] Kp = Kc (R T)n n = [+]-[+]

k1 k2

G

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+ +

G = G0 + RTln Q = G0 + 2,3RTlog Q Q (quotient) = [] [] / [] [] Q = 1 ln1 = 0 G = G0 + RT0 = G = G0

G

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, G = 0 Q = Kc G = G0 + RTln Q 0 = G0 + RTln Kc G0 = -RTlnKc = -2,3 RTlogKc Kc = 10- G

0/2,3RT

Kc lnKc G0 ( )

>1 + - >

=1 0 0 =

G

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: Q c

G = G0 + RTln Q = -RTlnKc + RTln Q Q < Kc lnQ < lnKc RTln Q < RTln Kc G < 0 () Q > Kc lnQ > lnKc RTln Q > RTln Kc G > 0

( )

G0 = -RTlnKc

G, G, Q Kc

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G

-G

Q = 1 Q = Kc

G

G Kc G >0

G = G0 + RTln Q

Q

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G, G, Q Kc G = G0 + RTln Q

G

Q = Kc Q = 1

Q

=25 C

G -G

Le Chatelier

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, ,

CO(g) + 3H2(g) CH4(g) + H2O(g) = -206,2 G= -141,9 kJmol-1

CO H2 CO H2 C4 H2 C4 H2 ( )

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[Co+2Cl4]-2 + 6H2O [Co(H2O)6]+2 + 4Cl-

Kc

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0 - TS0 = G0 = - RTlnKc lnKc = - 0/RT + S0/R (y = x + ) 1, 2 (P ): lnK1 = - 0/RT1 + S0/R lnK2 = - 0/RT2 + S0/R : ln (K2/1) = - 0/R (1/2-1/1) Vant Hoff

T, S

: 1/ lnKcKc

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T(C) 200 atm 400atm 600atm 800atm 1000atm 200C 90 96 97 98 99% 300C 64 76 82 88 92 400C 39 55 65 73 80 500C 20 32 43 51 57 600C 8 16 24 28 32 700C 4 9 12 15 16

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

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(pH=7) (N, native, folded) (D, denatured, unfolded)

Kc=Keq =[D] / [N]

ln (K2/1) = - 0/R (1/2-1/1) 0 = +533 kJ/mol ( )

T (C) 51 53 54.5 56 58 59 61 Keq 0,04 0,12 0,27 0,68 1,9 5 21

1) 0:

2) G0 54,5C:

G0= -RTlnKeq = -8,314 327,5 ln 0,27 = +3,56 kJ/mol

#2

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3) S 54,5C:

G = - TS S = - (G - H) / T = - (3,56-553) / 327,5 = +1,62 kJ/mol

T>58C, S G

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: O2

S>0 S

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() () (.. Krebs cycle)

: < 1000 Da

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-CoA

.. , :

G (coupled)

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1+2:

+ Pi + ATP 6-- + ADP + Pi + ATP 6-- + ADP

G03 = G01 + G02 = 5+ (-8) = - 3 kcal/mol G0

G0

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[+] 10-7 1 (pH=0)! [H2O]=1000/18=55,6 , = 1 1 [ ] : 1 mM Mg+2

: (steady state) (equilibrium)!

pH G0 (25C)

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+ : - + + Keq = Keq[H+] [] = [-] = 1 Q = [H+] G0 = G0 + RTln[H+] = G0 2,3RT(-log[H+]) = G0 -1371pH ( cal/mol)

+ : - + + Keq = Keq/[H+] G0 = G0 + RT ln 1/[H+] = G0 - RTln[H+] = G0 +1371pH ( cal/mol)

Keq G0

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R = 8,315 Jmol-1K-1 = 1,987 2 cal mol-1K-1 ln a = 2,303 log a 2,3 log a

G0 25C, pH=7

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G0 (25C, pH=7)

, G ( ) [ , ADP, Pi (1 )

~1-5mM ADP]

ATP

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G : 1)

()4-

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2) Pi ! ( , Pi):

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3) AD + ( pH = 7) 4) (D Pi)

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1) (1 ) 2) ( Pi

PPi AMP) (2 )

: ATP ( GTP): DNA mRNA , G-proteins

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(-P32-) (-PO42-)

-

-

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. , ! !

R R

R

: .. , , Na/K ATP ( ) : .. : , , DNA/RNA : .. ATP ( )

ATP Mg+2

70 : 1 mM Mg+2

Mg+2 DP

Mg+2 G0 (pH = 7 T = 38 C)

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Mg+2 [G0] ( ) pMg = -log[Mg+2] = 3 1 mM Mg (10-3 g)

= 2 10 mM Mg g (5-10 mM)

pH G0 (37 C)

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pH [G0]

pH7, G0~5,7 kJ ( )

( pH 6-7),

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( )

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: ) () ) Pi

1,3-

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Pi

(1,3 BPG) (3 PG)

(-12 kcal/mol)

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Pi

PCr Cr

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ADP + PCr ATP + Cr, G0= -3 Kcal/mol (CK)

, [PCr]=30 mM, 10 ATP

-CoA

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(CoA)

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( .. = GTP CTP TTP)

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2800 cal/day 50% 1400 12 cal mole ATP (..) 117 moles/day 117 x 551 (MW)= 64,5 Kg 50 g! 1: ~1300

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: [] + [DP] /[ATP]+[ADP]+[AMP] ( ) : 0 ( ) 1 ( ) 0,78

- - #2 ()(Internal energy, U) - : Hess , , CO : S #2 :Slide Number 30 S0 Gibbs G S NaCl G G G G, G, Q KcG, G, Q Kc Le Chatelier Kc #2Slide Number 52 G (coupled) G0 pH G0 (25C) Keq G0G0 25C, pH=7G0 (25C, pH=7)ATP Slide Number 65Slide Number 66 ATP Mg+2 Mg+2 G0 (pH = 7 T = 38 C) pH G0 (37 C) 1,3- -CoA (CoA)G

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Χ. ΚΡΟΥΠΗΣ Χημική Θερμοδυναμική (E-class)