Topic 9 Redox Processes (electrochemistry) and Topic 19 (more) Electrolytic cells

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what is an oxidation/reduction reaction (redox reaction)

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what is an oxidation/reduction reaction (redox reaction)

any chemical relation that involves a shift of electron denisty from one atom to another

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what are the old definitions for reduction and oxidation

oxidation: where a substance COMBINES wtih oxygen

ex. 2Mg + O2 → 2MgO

CH3OH + O2 → 2CO + 2H2O

reduction: REMOVAL of oxygen or addition of hydrogen

NiO + C → Ni + CO (smelting, Ni has been reduced, removed oxygen)

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what are the new definitions for reduction and oxidation in terms of electron transfer

LEO GER

oxidation: loss of electrons

reduction: gain of electrons

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what is a reducing agent

electron SUPPLYING substance during a redox reaction, LOSES electrions

  • causes other substance to be reduced

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what is an oxidizing agent

electron ACCEPTING substance, gains electrons

  • causes otehr substance to be oxidized

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what is an oxidation number

the charge an atom in a compound would have if the electrons in the bond belonged ENTIRELY to the more electronegative atom

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how can oxidation numbers be used to identify the oxidation/reduction half reactions and the RA and OA

if theres a DECREASE in oxidation state PER ATOM, it is reduced, and acts as the OXIDIZING agent

if theres an INCREASE in oxidation state per atom, it is oxidized, and acts as a REDUCING agent

** if there is no change in oxidation numbers PER ATOM, it was not a redox reaction

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what are the oxidation # rules for a monatomic ion and element

O# for monatomic ion is equal to the CHARGE of the ion

O# for element is ZERO

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what are the oxidation # rules for alkali (group 1) and alkaline earth (group 2) family atoms in a compound

o# for alkali group 1 in a compound is +1

o# for alkali earth metals in a compound is +2

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what are the oxidation # rules for oxygen and hydrogen in a compound

o# for oxygen in a compound is -2 ** except peroxides which are -1 (O2 2- = perioxide = -1)

o# for hydrogen is +1 ** except hydrides = -1 (when combined with a metal)

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what are the rules for flourine or halogens

o# of flourine is ALWAYS -1 (because most electronegative)

o# of halogens are always -1 except when bonded with oxygen or a halogen higher up in the group (ClF, F = -1, Cl = +1)

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what are the oxidation rules for compounds or a total reaction

all the TOTAL oxidation numbers for the elements making up a compound/ion must add up to the CHARGE of the compound

the NET change in TOTAL oxidation numbers for a reaction must be ZERO

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what are the 7 steps to balancing redox reactions with acidic solutions

  1. divide into half reactions

  2. balance atoms OTHER than oxygen and hydrogen

  3. balance O atoms using H2O

  4. balance H atoms using H+

  5. balance net charge in each reaction using e-

  6. balance number of e- gained and lost by multiplying, then ADD two half reactions

  7. cancel out anything that is the same on both sides

DONE!

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what are the extra steps needed when balancing redox reactions with basic solutions

  1. add the same number of OH - ions as there are H+ ions to BOTH sides of the equation

  2. combined any OH- and H+ to form H2O

  3. cancel out any H2O molecules you can

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how is a redox table set up

on the top right, you have the strongest reducing agent RA, then weaker as you go down (metal elements)

on the bottom left, you have the stongest oxidizing agent OA, then weaker as you go up (metal ions)

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what is the spontaneity rule using a redox table

it is spotaneous if… going from the OA to the RA, it is UP and to the right

it is NON-spontaneous if… going from the OA to the RA it is DOWN and to the right

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what are the 5 steps to predicting redox reactions (if spontaneous or not)

  1. identify each atom/ion as an oxidizing agent or reducing agent (write above or below)

  2. choose the strongest OA, and write the equation for its reduction

  3. choose the strongest RA, and write the equation for its oxidation

  4. balance the number of electrons lost/gained by multiplying, then add the 2 half reactions

  5. use the spontaneity rule for the reactant OA and RA, to see if it’s spontaneous

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what are redox titrations

similar to acid/base titrations: used to determine the unknown concentrations of a substance, based on the redox reactions (electrons transferred instead of protons like with acids)

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what is an indicator for in redox titrations

used to signal the equivalent point (equimolar), some redox reactions have their own colour change, thus additional indicator is not needed

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when are redox titrations used/applications

food & beverage, pharmaceutical, water and environmental analysis

  • ex. vitamin c content of foods, detection of sulfur diocide in wine, iron conctent in supplements, concentration of chlorite in bleach

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what is the biological oxygen demand (BOD)

defined as the amount of oxygen needed to decompose organic matter over a specific time at a specific temperature

  • used to measure the degree of pollution in water

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what is the relationship between BOD, waste matter, dissolved oxygen, and pollution

high BOD = more waster = lower dissolved O2 levels = MORE POLLUTED

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what is parts per million (how do you get it)

1 ppm = mass of solute in mg / volume of solution in dm³

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whar are the reactions and final ratio that make up the winkler method

2Mn 2+ + O2 + 4OH- → 2 MnO2 + 2 H2O

MnO2 + 2I- + 4H+ → Mn 2+ + I2 + 2H2O

2S2O3 2- + I2 → 2 I- + S4O6 2-

OVERALL: 1 mol O2 → 4 moles S2O3 2-

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what are the values of BOD for normal water, poor quality water, and sewage

normal = BOD < 1 ppm

poor = 20 ppm

sewage = 350 ppm

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what is the winkler method

3 steps, used to measure dissolved oxygen in water

  1. MnSO4 excess is added, to “fix” oxygen into MnO

  2. iodide ions are oxidised by MnO, causing iodide normal atoms

  3. I2 is titrated with Na2S2O3

OVERALL: for every 1 mol of O2, 4 mols of S2O3 2- are used (1:4)

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what do voltaic / galvanic cells do

produce electricity through spontaneous redox reactions

cell potential is measured in volts with a voltmeter (1V = 1 J/C)

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what are the parts of a voltaic cell

split into 2 parts connected by a salt bridge

  • each part has an electrode (metal) and its corresponding electrolyte (metal ion)

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what are the functions of the salt bridge

  1. physical separation between the cathode/ anode (between metal electrodes)

  2. path for ions to flow to complete the circuit

  3. reduces liquid junction potential (aka voltage reduction when 2 liquids touch)

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what is the notation for a voltaic cell

(for zinc and copper)

<ul><li><p>includes the oxidation = anode, then reduction = cathode (each in diff half cells)</p></li><li><p>the metal for the anode is most reactive</p></li></ul>
  • includes the oxidation = anode, then reduction = cathode (each in diff half cells)

  • the metal for the anode is most reactive

<ul><li><p>includes the oxidation = anode, then reduction = cathode (each in diff half cells)</p></li><li><p>the metal for the anode is most reactive</p></li></ul>
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draw and label a voltaic battery with zinc and copper

<p>should include…</p><ul><li><p>1 molar zinc nitrate, zinc 2+ ions</p></li><li><p>1 molar copper nitrate, copper 2+ ions</p></li><li><p>ammonium nitrate salt bridge</p></li><li><p>electrolytes, solutions, voltmeter</p></li><li><p>show movement of the ions and electrons</p></li><li><p>LABEL: anode (neg because electron build up), oxidation, salt bridge, cations (towards the cathode), anions (towards the anode), cathode, reduction</p></li></ul>

should include…

  • 1 molar zinc nitrate, zinc 2+ ions

  • 1 molar copper nitrate, copper 2+ ions

  • ammonium nitrate salt bridge

  • electrolytes, solutions, voltmeter

  • show movement of the ions and electrons

  • LABEL: anode (neg because electron build up), oxidation, salt bridge, cations (towards the cathode), anions (towards the anode), cathode, reduction

<p>should include…</p><ul><li><p>1 molar zinc nitrate, zinc 2+ ions</p></li><li><p>1 molar copper nitrate, copper 2+ ions</p></li><li><p>ammonium nitrate salt bridge</p></li><li><p>electrolytes, solutions, voltmeter</p></li><li><p>show movement of the ions and electrons</p></li><li><p>LABEL: anode (neg because electron build up), oxidation, salt bridge, cations (towards the cathode), anions (towards the anode), cathode, reduction</p></li></ul>
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what is electrolysis

process where electrical energy is used to drive a non-spontaneous redox reaction

often used to purify metals, especially for metal ions that are poor oxidizing agents

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what is an electrolytic cell

it has a single container, 2 electrodes (anode, cathode) a solution (electrolyte), and a battery/ source of electricity

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what is a molten electrolytic cell

created by passing electricity through an ionic compound thats melted (LIQUID)

typically platinum electrodes are used as they are inert, don’t contribute to the overall redox reaction

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explain how molten cells work (Pt | NaCl | Pt)

because of the battery, the electrons create the neg side = the cathode (reduction), the pos is the anode

at the cathode: Na + ions get electrons from the Pt strip, then form the solid Na

  • metal reduce at cathode

at the anode: Cl - ions lose electrons to the Pt strip, become Cl gas bubbles

  • non metal oxidized at anode

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what are the similarities and differences between voltaic and electrolytic cells

similarities

  • both have electrodes

  • oxidation at anode, reduction at cathode

differences

  • voltaic: anode is neg because electrons build up because of oxidation (loss of electrons). electrolytic: CATHode is neg because of electrons coming from neg. end of battery

  • voltaic: not touching, 2 solutions, bridge. electrolytic: one solution, no bridge

  • voltaic: spontaneous. electrolytic: non-spont. needs energy

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how does electrolysis of an aqueous solution work

passing current of electricity through an aquenous (dissolved in water) ionic compound / salt with an electrolytic cell

  • more difficult to predict the redox half reactions because water molecules can also be reduced/oxidized

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describe the parts of the electrolysis of aqueous sodium chloride

Pt | NaCl (aq) | Pt

  • battery, with cathode neg (reduction), anode pos (oxidation), platinum electodes

  • one container with aqueous solution

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how do you determine the cell potential of a cell

always E cell = E reduction + E oxidation

  • to find E oxidation, use DB, but must FLIP SIGN (because shown ones are for reduction)

  • for electrolysis of aqueous solutions, remember to write out all possible reduction reactions, pick the LEAST neg (most spontaneous) option, do the same for the oxidation

    • then multiple and add to create the overal reaction

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what does the sign of the cell potential mean

negative is non-spont, (electrolytic)

pos is spontaneous (voltaic)

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what are the factors that determine the possible redox reactions in an electrolytic aqueous cell

MAINLY relative reactivity (from DB)

  • less neg = more reactive/spont

but also depends on their concentrations

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what are the applications of electrolytic cells

  • refining metals (copper, aluminum, mangesium)

  • electroplating (putting a metal on the surface of something)

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what are the 3 main functions electroplating

  1. make something more attractive (chrome plating car bumper)

  2. prevent rusting of steel (galvanizing/ plating zinc onto iron)

  3. jewelry (gold plating)

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how does electroplating work/ what are the parts / describe the diagram

<ul><li><p>battery, neg end is cathode, connected to object you want plating ON</p></li></ul><ul><li><p>cathode is reduction, where positive metal ions go onto the object, to join with electrons</p></li><li><p>anode has material you want to use (silver bar). oxidation occurs, resulting in creation of metal ions</p></li><li><p>solution of aqueous ionic compound (ex. silver nitrate)</p></li></ul>
  • battery, neg end is cathode, connected to object you want plating ON

  • cathode is reduction, where positive metal ions go onto the object, to join with electrons

  • anode has material you want to use (silver bar). oxidation occurs, resulting in creation of metal ions

  • solution of aqueous ionic compound (ex. silver nitrate)

<ul><li><p>battery, neg end is cathode, connected to object you want plating ON</p></li></ul><ul><li><p>cathode is reduction, where positive metal ions go onto the object, to join with electrons</p></li><li><p>anode has material you want to use (silver bar). oxidation occurs, resulting in creation of metal ions</p></li><li><p>solution of aqueous ionic compound (ex. silver nitrate)</p></li></ul>
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what are the factors that affect the amount of product formed on the electrodes during electrolysis

  1. current

  2. duration of electrolysis (longer = more)

  3. charge of the ion

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what is the important equation used to determine the time required to deposit a metal onto an object and the variables

n e- = I * t / F

n e- = # of moles of electrons

I = current in Amperes (1 A = 1 c/s)

t = time in seconds

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what does the change in gibbs free energy mean in relation to spontaneity

negative Δ G = spontaneous (E cell +, voltaic)

positive Δ G = non-spont (E cell -, electrolytic)

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what is the cell potential, gibbs free energy and type of reaction of a dead battery

cell potential = zero, gibbs free energy = zero,

reached equilibrium, no reaction

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