Bio-electrochemistry Flashcards

1
Q

electron transfer chains

A

overal chemical reaction takes place by a series of electron transfers betwen molecules

in the mitochondria, the electron transfer occurs with an iron ion, Fe3+ + e- –>–< Fe2+

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2
Q

reduction potential

A

a measure of the work dine/used by the reaction
- can be measured using electrode potentials

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3
Q

half cell for reduction of oxygen

A

4e3- + o2 + 4h+ –> 2h2o

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4
Q

half cell for oxidation of nadh

A

nadh –> nad+ +h+ + 2e-

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5
Q

during photosynthesis, the electron transport chains pt 1

A
  1. NADH dehydrogenase - nadh –> nad+, 2e- leaving to go to ETC, H + pumped across membrane
  2. ubiquinase = UQ, transfers e- within membrane to cytochrome C - the transfer of e- from UQ –> cytochrome BCL releases energy to pump h+ ions across matrix to IMS
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6
Q

during photosynthesis, the electron transport chains pt2

A

cytochrome C is ETC, with fe3+ ion, fe3+ + e- -> fe2+ cc

this transfers electron to cytochrome C oxidase, which is where oxygen accepts electrons from the protein to form h2o
- this releases energy to pump H+ across membrane

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7
Q

during photosynthesis, the electron transport chains pt3

A

at this point, there is a high concentration of H+ ions in IMS, creating an electrochemical gradient

the H + moves down conc gradient via chemiosmosis through atp synthesis, releases energy for condensation reaction of ADP +PI –> ATP

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8
Q

electrochemical cells

A

consists of 2 half cells and measuring the difference between PD via simple redox reaction

zn(s) + cu2+ (aq) –> cu(s) + zn2+(aq)
- the zinc is oxidised losing 2e- and so dissolves
- copper is reduced, gaining 2e- and precipitates

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9
Q

drawing electrochemical cells

A

on the left
- have the beaker with reaction that is oxidising , with metal electrode and solution of metal ions - zinc loses 2e- when oxidising, so electrons flow to wire to copper, zn2+ joins solution

on right
- beaker with reduction reaction, as copper recieves electrons from zinc, cu2+ in solution joins to for cu on electrode

also got a salt bridge to ensure charge stays sameand ions flow to complete circuit

measuring using voltmeter

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10
Q

salt bridge

A

glass tube filled with saturated kcl

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11
Q

electrochemical cell notation

A

Zn(s)|Zn2+(aq)|| cu2+ (aq)|cu(s)

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12
Q

types of half cell - 1

A

metal electrode in a solution of its ions

cu2+ +2e- –> –< cu

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13
Q

types of half cell - 2

A

gas in contact with solution of its ions - hydrogen electrode - uses platinum electrode as inert
2h+ +2e- –>–< h2

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14
Q

types of half cell - 3

A

two different oxidation states of same soluble species - found usually in biological systems

fe3+ e- –>–< fe2+
using pt electrode

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15
Q

types of half cell - 4

A

metal in contact with an insoluble salt

agcl +e- –> ag(s) + cl-

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16
Q

standard conditions with electrochemical cells

A

1M, 1 arm, pure substances, inert pt electode, 298K

17
Q

cell reactions

A

they are all written as reduction reactions
- the positive E cell voltage has a greater reductive power, so thats the one reducing, the other one generally negative is the oxidising one.

RH = reducing
LH = oxidising

Ecell = RH-LH

18
Q

standard hydrogen electrode

A

This can be used to work out one half cell
hydrogen electrode is the LH, oxidising one

19
Q

free energy relationship

A

delta G = -nFEcell

n = number of electrons transferred in half cell

F = faradays constant = 96485C mol-1

20
Q

E cell and free energy

A

when E cell is positive (reduction) delta G is negative so spontaneous

when E cell is negative (oxidation), delta G is positive so not soon

when E cell = 0, no overal voltage so delta G = 0, battery is dead

21
Q

Nernst equation

A

the relationship between electrode potential and concentration

allows us to convert between non standard and standard conditions

for a half cell: xOx + ne- –> yRed
E = E^o + RT/nF x ln[ox]x/[red]^y

E = new potential
E^o = standard reduction potential
R = gas constant = 8.3143jk-1mol-1
T = temp in K
n = number of electrons transfered

22
Q

if things are in its standard state

A

it can be ignored and given the value of 1/ any solid

23
Q

nernst equation for a cell

A

produced by substracting 2 half cell nernst equations

becomes E = E ^o + RT/nF x ln [RHaq] /[LHaq]

24
Q

for hydrogen ions standard state

A

[H+] = 10-7

25
Q

how to know when to use nernst or not

A

if H+ is not involved, then regular way is fine

if H+ is involved,need to use Nernst equation

26
Q

selective transport

A

across membranes is important as it power much of cellular machinery, using embedded membrane bound proteins to pump ions across membranes

27
Q

cells and membrane potential

A

cells are always electroneutral, so charge inside and outside cell need to be opposite

this is why concentration gradients work as ion travel across the membrane for this

28
Q

Membrane potential

A

calculated using H+ ion electrochemical cells
- no hydrogen gas in biological systems, so displaying the transport of protons across the membrane rather than transfer of electrons

H+out –> H+ in

29
Q

example - potential difference across biological membrane

A

RH E =E^o + RT/nF x ln [H+out}/pH2^1/2

LH E =E^o + RT/nF x ln [H+IN}/pH2^1/2

THEREFORE. E =RT/nF x ln [H+out]/[H+in]

30
Q

E cell and electrical potential

A

E cell describes a redox potential difference electrical potential
- a neg elec potential indicates that the inside of the cell is negatively charged compared to the outside

31
Q

electrical potential equations

A

E = RT/nF x ln[H+] out/[H+]in - electrical potential

delta G =RT x ln [H+]in/[H+]out + Fx electrical potential

32
Q

proton motive force

A

driving force for protons, the transfer of H+ across a membrane produces a free energy change.

promotes the movement of H+ ions across membranes down the electrochemical gradient

For protons, the electronic potential equation simplifies to:
delta G = 2.303 RT (pHout - pH in) + F electrical potential

33
Q

the proton motive force equation

A

delta G h+ = -F delta P

delta P = proton motive force

34
Q

glass pH electrode

A

allows to measure changes in cell voltage that are due to changes in membrane potential

the thin glass membrane holds H+ in, this is dipped into a solution with unknown H+ out

the voltage is measured across the thin glass membrane

this works as the membrane has SiO2 - protonatable sites

measures pH of test solutions
given symbol E*

35
Q

Nernst slope

A

Ecell = E* - kpH
y = c-mx
ph = x
m= k
E* = c

E=const = 2.303RT/nF pH

2.303rt/f TERM = 0.0591V at 298k therefore K = 0.0591

36
Q

generalising this equation to other ions

A

E = RT/zF x ln [Mz+]out/[Mz+]in - eletrical potential

delta G = RTln[Mz+] in/[Mz+]out + zF electrical potential

z =the charge of the ion
z is -ve for -ve ions, +ve for +ve ions

37
Q

spontaneous electron transfer positive

A

passed from E more negative to E more