Exam 1 Flashcards
Change in Enthalpy
🔺H=🔺G+T🔺S
🔺H must be <t>
</t>
Standard Gibbs Free Energy
Chemical : 🔺G0 @ T=25oC and pH=0
Biological : 🔺G0’ @ T=25oC and pH=7
Using Gibbs Free Energy
For reversible reaction: A+B yields Y+Z
🔺G=🔺G0’+RT ln[Y][Z]/[A][B]
@ Equilibrium 🔺G=0 and ratio=Keq
Therefore
🔺G0’= - RT ln Keq
Coupled Reactions
Use free energy released by an exergonic reaction to drive second energonic reaction.
Reduction of Pyruvate
Endergonic
Pyruvate + 2H++2e- —> Lactate
🔺G0’= 36 kJmol-1
Reduction of NADH/H+
Exergonic
NADH + H+—>NAD++2e- +2H+
🔺G0’ = -62 kJmol-1
Coupled Reaction
Exergonic
Pyruvate + NADH + H+—> NAD++ Lactate
🔺G0’ = -26 kJmol-1
Activation Energy
Ea
Amount of energy required to bring all molecules in a mole of reactant at a given temperature to a reactive state.
Increasing T decreases Ea by increasing kinetic energy of all molecules.
Adding enzyme reduces Ea and increasses reaction rates by 103 to 107 times.
Covalent Bonds
1) Van der Waals
2) Hydrogen
3) Ionic
4) Hydrophobic Bonds
1) Interaction between dipolar molecules
2) Sharing of electrons between dipolar molecules
3) Anion/Cation bonding
4) Non-polar water-averse regions or molecules.
Weak Bonds and Temperature
Affects and Consequences
Increasing Temperature
- weakens Hydrogen, Van der Waals, and Ionic bonds
- strengthens Hydrophobic bonds
Consequence: denaturing of 3D structures (DNA, proteins, membranes)
Can lead to clumping/strengthening of hydrophobic elements.
Water
Unique - Covalent and Polar
Hydrogen bonds inividually weak (1-5 kcal to break 1 mole)
Overall effects are strong - high melting/boiling points and high surface tension/cohesion.
Colligative Properties
Depend on concentration of solute(not size or type)
Increasing solute concentration of water increases boiling point, vapor/osmotic pressure, and reduces freezing point.
Rate of diffusion
Rate (dQs/dt) depends on solute size, electrical charge and solubility.
dQs/dt = P(C1-C2)
P=permeability constant (cm/s)
Partition coefficient (K)
K=[solute]lipid/[solute]water
pH
pH = -log[H+]
In pure water at 25oC, pH = 7
Strong Acids and Bases
vs
Weak Acids and Bases
Strong - readily release ions
Weak - are only partially ionized under biological conditions
Dissociation of Acids -
1) General Formula
2) pK
3) Consequences
1) HA <=> H+ + A-
2) pK = -log10Keq = pH at which [A-] = [HA]
3) pK (pH at equillibrium) is low, ex: <3 for HCl and Sulfuric Acid
Henderson-Hasselbach equation
pH = pK + log[A-] / [HA]
pH importance
Low pH means [H+] is high, amino and carboxyl protonated (valence electron is positive).
High pH means [H+] is low, amino and carboxyl groups ionized(valence electron is negative).
Buffers
1) What are they?
2) Adding Acid
3) Limits
4) Ideal conditions?
1) Usually weak acids
2) Liberated protons can bind with buffer and effect is reduced
3) Will only work over limited pH range
4) When pH=pK because half of buffer works against each direction of pH