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Solution Manual For Biochemistry Concepts and Connections 1St Edition by Appling Anthonycahill and Mathews Isbn 0321839927 9780321839923
Solution Manual For Biochemistry Concepts and Connections 1St Edition by Appling Anthonycahill and Mathews Isbn 0321839927 9780321839923
Solution Manual For Biochemistry Concepts and Connections 1St Edition by Appling Anthonycahill and Mathews Isbn 0321839927 9780321839923
Chapter 03
1. a.
DG = DH - T DS
kJ kJ kJ
ΔG° = −280 − ( 298 K ) −0.790 = −44.6
mol mol × K mol
ΔG° = ΔH ° − T ΔS°
kJ kJ
ΔG0 = 0 = −280 − ( x K ) −0.790
mol mol × K
−354.4 K = −x
2. a. Reversing the direction of the reaction as written requires a reversal of the sign on ΔH. Also,
when summing two or more reactions, the species that appear on both sides cancel; thus:
b. The reaction has two O-H bonds broken; therefore, the energy of a single O−H bond is 926/2 =
463 kJ mol−1.
b. The decomposition products are both gasses, and therefore have significantly more translational
and rotational freedom compared to the initial solid. Thus, entropy increases.
4. a. ΔG° = ΔH° − TΔS°
= (−2816 kJ mol−1) – (310 K)(0.181 kJ K−1 mol−1)
= –2872.1 kJ mol−1
This G6P concentration is never reached because G6P is continuously consumed by other reactions,
and so the reaction never reaches true thermodynamic equilibrium.
7. a. ΔS must be positive because the increase in isoenergetic conformations in the denatured state
increases the entropy of the denatured state relative to the folded state.
8. This process reduces the entropy of the solvent water, which becomes more ordered in the clathrate
structures. This is the hydrophobic effect.
b. In cases of cold denaturation, the sign on ΔS is dominated by the hydrophobic effect and is
therefore negative. In these cases, ΔH must also be negative (see Table 3.3) for the process to become
favorable as temperature decreases. Clathrate cage formation would account for the sign of ΔH being
negative (favorable) for cold denaturation.
If ΔH° and ΔS° are independent of temperature, a graph of lnK versus 1/T should be a straight line
with slope −ΔH°/R. These values can also be determined from direct fits to the K versus T data using
nonlinear curve-fitting software.
11. a. See Problem 10. Plot lnKw versus 1/T and fit a line to the points. The slope will correspond to
−ΔH°/R.
1/T ln Kw
0.00366 −34.4
0.00336 −32.2
0.00330 −31.9
0.00323 −31.3
K =e RT
= e 0.008314 2×98
K =17.6
b. The favored direction for the reaction can be determined by comparing K to Q. From part (a)
we know that K = 17.6. Q = 1/(0.001) = 1000. Thus, Q > K, and therefore the reverse reaction is
favored. This conclusion is also borne out by the (much more time-consuming) calculation of ΔG:
ΔG = ΔG°'+RTln
[G6P] kJ kJ
+ 0.008314 1 kJ
( )
= −7.1 298K ln = +5.93
[G1P] mol mol ×K 0.001 mol
kJ kJ kJ
ΔG = −7.1 +17.1 = +10.0
kJ kJ [oxaloacetate][0.0003][1]
0 > +29.7 + 0.008314 ( 310K )ln
mol mol ×K [0.0004 0.020][
−11.5 > ln
[oxaloacetate][0.0003][1] = ln (37.5[oxaloacetate])
[0.0004][0.020]
Thus, the reaction is unfavorable under these conditions when [oxaloacetate} exceeds 2.63 × 10−7 M.
Since,
ΔH° − TΔS° = −RTlnKeq
=0
Then,
ΔH° = TΔS°
= (323 K) × 904 J mol−1 K−1
= 292.2 kJ mol-1
15. c. Since both ΔH° and ΔS° are positive, the fraction denatured will increase with increasing
temperature.
16. a.
ΔG = ΔG°'+ RTln
[glucosein ] kJ kJ 0.0001 kJ
(310K )ln
=0 + 0.008314 0.00001 = +5.93
[glucoseout ] mol mol × K mol
Thus, > 1.94 × 10−7 mol ATP are required to drive the reaction in part (a) forward (i.e., to make ΔG <
0). No ATP hydrolysis is required for the reaction in part (b) as ΔG is already < 0.
17. a.
ethanol NAD+ CO2
ΔG = ΔG°'+ RTln 2
[ pyruvate][NADH ] H +
0.000350M 15torr
kJ kJ (ethanol ) 1M 750torr
−38.3 = −64.4 + RTln 2
mol mol 62×10−6 M 15×10−6 M 10−7.4 M
1M 1M 10−7.0 M
−6
kJ ( ethanol ) × ( 7.0 ×10 )
38.3 kJ 64.4 kJ 0.008314 (310K )ln
− =− +
mol mol mol 1.47 ×1010−
kJ kJ
+26.1 = 2.577 ln (ethanol )×(4.75×104 )
mol mol
kJ
26.1
mol
kJ
2.577
4 4
e mol
= ethanol × 4.75 ×10 = 2.50×10
( ) ( )
2.50 ×104
(ethanol ) = 4.75×10 4 = 0.527
Evaluation of ΔG°' requires combination of ΔG°' values for ATP hydrolysis (given) and glucose
oxidation (which can be calculated from the E°' info provided):
glucose → 2pyruvate + 6H+ + 4e− This is the e− donor with E°' = −0.590 V.
2NAD+ + 2H+ + 4e− → 2NADH This is the e− acceptor with E°' = −0.315 V.
NET: glucose + 2NAD → 2pyruvate + 2NADH + 4H+
+
ΔE°' = (−0.315 V) – (−0.590 V) = + 0.275 V
Thus, ΔG°' = −nFΔE°' = −(4)(96.5 kJ/mol × V)(+0.275V) = −106.2 kJ/mol.
glucose + 2NAD+ → 2pyruvate + 2NADH + 4H+ ΔG°' =−106.2kJ/mol
+
2ADP + 2Pi + 2H → 2ATP + 2H2O ΔG°' = + 61.0 kJ/mol
+ +
NET: glucose + 2NAD + 2ADP + 2Pi → 2pyruvate + 2ATP + 2H2O + 2NADH + 2H ΔG°' = –45.2 kJ/mol
kJ (62×10−6 )2 (0.0031)2 (1)2 (15×10−6 )2 (10−0.4 )2
ΔG = −45.2 + RTln
mol (0.0051)(2.2 × 10−4 )2 (0.0059)2 (3.5 × 10−4 )2
kJ kJ
ΔG = −45.2 + 0.008314 (310K )ln 1.2( 5×10−3 = −) 62.4 kJ
mol mol mol
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XXI.
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— Äääääää!
Rengit kuorsailivat lutissa, niin että seinät tärisivät. Kas, eikös ollut
Soittaja-Kimperi nukahtanut nurkan taakse pidellen toisella kädellään
vielä hanurin olkaremmistä. Oli tyhjennellyt pullojen pohjia ja siihen
väsähtänyt. Antaapa hänen nukkua. Iisakki meni jälleen pirttiin ja
raotti morsiuskamarin ovea. Vieläpähän nukkui Taava. Suu oli
auennut ja aurinko paistoi kitalakeen. Palavissaan oli Taava
potkaissut peitteen pois ja täyteläiset sääret olivat paljastuneet
yläpuolelle polven. Iisakki hymähti. Suloinenpa olikin Taava siinä
nukkuessaan, kun vaan olisi suunsa sulkenut. Kyllä pitäisi kiittää
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Nuusperi oli mennyt ja mitä varten hän oli pirullisia kuviaan kirjoihin
piirrellyt.
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Rietula kirosi.
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