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## PHYS CHEM BIOC I

by: Carmela Kilback

76

0

3

# PHYS CHEM BIOC I CHEM 452

Carmela Kilback
UW
GPA 3.92

Sarah Keller

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COURSE
PROF.
Sarah Keller
TYPE
Class Notes
PAGES
3
WORDS
KARMA
25 ?

## Popular in Chemistry

This 3 page Class Notes was uploaded by Carmela Kilback on Wednesday September 9, 2015. The Class Notes belongs to CHEM 452 at University of Washington taught by Sarah Keller in Fall. Since its upload, it has received 76 views. For similar materials see /class/192557/chem-452-university-of-washington in Chemistry at University of Washington.

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Date Created: 09/09/15
Example As mentioned earlier entropy is challenging to measure in the lab How can we rewrite a change in entropy AS in terms of variables that are easier to measure like T and V Here STV Assume any transition is reversible and that there is only PV work in the system Since entropy is a state function we can write it as follows 95 85 dS dT dV 8er avlr The second partial differential is one of the Maxwell relations BS 9P d5 dT W W Karl How do we get rid of the S in the first partial derivative Multiply by 1 TT is 1a Cv 3T V T dT V T dT V T Substituting in to the whole equation C 9P d5 V dT dV T W And integrate T C V 9P AS VdT dV Jr liar which is much better we can find all of these in a table or in the laboratory Example Using the equation above find AS when n moles of an ideal gas go from Ti Vi to Tf Vf given CV For an ideal gas BF9TV nRV T C V R AS j Vdn jn dv T T V V AS CvlnT Ti nR1nV Vi Example Here we finally show explicitly that for an ideal gas E is only a function of T From very early on in this course we ve been saying that for an ideal gas E is only a function of T We used it extensively to show that for an ideal gas that H is only a function of T and also that CP CV nR Now let s imagine that E could be a function of another variable as well like volume which makes sense because there is a PdV in the equation for dE Our method will be to show that all dependence on volume disappears 77 2008 Sarah L Keller So suppose that EVT 9E 8E dE Elc Because E is a state function T68 P8VJ dV CVdT Using 8E TaS MW and CV for ideal gas T army 8T 9P T PJdV CVdT Using a Maxwell relation V J PJdV CVdT Using PV 2 nRT V P PdV CVdT 0dV CVdT CVdT So E isn t a function of V at all only ofT 8E What if you have a van der Waals gas instead of an ideal gas Then t 0 T 2 Example Find BE8VT exactly for a van der Waals gas for whichLP QJV nb nRT BE 1 TBS P8VJ fromBETBS P8V lavlr lad T Tla Sl Fla VJ 9V T 9V T 9P T i P by a Maxwell relation V nR nRT n2 nRT n2 T a 2 from P a 2 V nb V nb V V nb V quot2 Maybe this would be an interesting way to measure the constant a in the laboratory 78 2008 Sarah L Keller Errors of Fact in Chapter 3 of the 3rd edition of Tinoco et a From Mickey Schurr We have now reached the end of Chapter 3 in T inoco et ul Just for the sake of completeness here are some descriptions of things that Mickey Schurr found were wrong in the text at least for the 3rd edition 1 In Table 31 it is indicated that urea forms a dimer with a single H bond in H20 which process is supposed to have a AHquot of 5 kJmole In fact spectroscopic measurements show no sign of any H bond dimer in this system under conditions where a cyclic lactam does not show such a spectroscopic signature Urea does show evidence for a very weak association in water but it most likely involves stacking with anti parallel dipoles rather than H bond formation 2 In Table 32 it is indicated that polyglutamic acid undergoes a helix coil transition in aqueous solution under any conditions but it requires considerable time to aggregate possibly because the kinetics of association are retarded by the high electric charge All of the data on the helix coil transition of polyglutamic acid are skewed and irrelevant because of this phenomenon It is mentionable that for macromolecules whether charged or not there is always a condensed phase with stability very close to that in the liquid phase Solubility of a macromolecule even when charged is at best marginal 79 2008 Sarah L Keller

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