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Electrochemistry
 study of chemical reactions/changes Electrolytic cell:
accompanied by the production of current
and the consumption of electrical energy
 electrochemical reactions are reduction-
oxidation reactions that involve the
transfer of electrons

Parts of an electrochemical cell:

 electrodes – where current enters or exits
o inert electrodes – does not
participate in electrochemical
reaction
 anode – where oxidation (loss of electrons)
occur
 cathode – where reduction (gain of Example: Molten NaCl (Down Cell)
electrons) occur  Overall reaction
o
Helpful mnemonics:
 Cathode(-) half – reaction (reduction)
 AN OX ate a RED CAT (anode – oxidation,
reduction – cathode) o
 OILRIG – oxidation is loss, reduction is gain  Anode (+) half – reaction (oxidation)
o
2 kinds of electrochemical cells:
 Direction of electrons – from anode (+) to
 Electrolytic cells – non-spontaneous
cathode (-)
electrochemical reactions (electrolysis),
external energy source (direct current)
Example: Electrolysis of Aqueous IA salts (NaCl, KI,
needed
etc.)
o negative anode, positive cathode
 Overall reaction
 Voltaic or galvanic cells – spontaneous
electrochemical reactions produce electric o
energy (e.g. batteries)
o positive cathode, negative anode  Cathode(-) half – reaction (reduction)
o
2 kinds of electric conduction:
 Anode (+) half – reaction (oxidation)
 metallic conduction – electron flow with no
atomic motion o
 ionic/electrolytic conduction – electron flow  Direction of electrons – from anode (+) to
accompanied by ionic motion cathode (-)
o cations  negative electrode Exercise: What would be the anode half – reaction
o anions  positive electrode for the electrolysis of KI?
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passge of 3.20 A of current through a solution of

Example: Electrolysis of Aqueous Sodium Sulfate Pd(II) sulfate for 30.0 minutes.
(Electrolysis of Water)
 Overall reaction Solution:
 Electrochemical reaction:
o

 Electrical charge passed through the cell =

o
(3.20 A)(30.0 min)(60 s/1 min)=5760 C
 Cathode(-) half – reaction (reduction)
 moles of electrons = (5760 C)(1 mol e-
o /96,485 C) = 5.97 X 10-2 mol
2 ( )−  moles of Pd metal formed = (5.97x10-2 mol
e-) x (1mol Pd/2 mol e-) = 2.98x10-2 mol
 Anode (+) half – reaction (oxidation)  grams of Pd = 2.98x10-2 x 106.4 g/mol =
o 3.17 g
 Direction of electrons – from anode (+) to
cathode (-) Other sample problems:
 and ions are just supporting
electrolytes 1. An electrolytic cell contains 50.0 ml of a
0.152M FeCl3 solution. A current of 0.620 is passed
Other notes about electrolytic cells: through the cell, causing deposition of Fe(s) at the
 Molten salt or electrolyte solution serves as cathode.What is the concentration of the Fe+3 in
current-carrying medium the cell after this current has run for 20.0 min?
 Electrochemical reactions can be predicted
2. A current is passed through a 500.0ml solution of
by comparing reduction potentials
CaI2. The following electrode reactions occur:
 Electrode may participate in
electrochemical reactions Anode:
Cathode:
Coulometry After some time, analysis of the solution shows that
37.5 mmol of I2 has been formed.
Faraday’s Law of Electrolysis: During electrolysis,
(a) How many faradays of charge have passed
one Farady of electricity reduces and oxidizes,
through the solution?
respectively, one equivalent of the oxidizing agent
(b) How many coulombs?
and the reducing agent.
(c) What volume of dry H2 at STP has been formed?
d) What is the pH of the solution?
 1 faraday of electricity = 6.022 X 1023
electrons
 1 Ampere (A) = 1 Coulomb per second
 1 Faraday = 96, 485 C ≈ 96,500 C
Voltaic/Galvanic Cells
Sample Problem: Calculate the mass of Pd
produced by the reduction of Pd(II) ions during the
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Notation example:  (Li, K, Ca, Na) > Mg, Al, Mn, Zn, Cr, Fe, Cd,
Zn |Zn2+(1M) || Cu2+(1M) | Cu Co, Ni, Sn, Pb, H, Sb, Cu, Hg, Ag, Pt, Au
half cell 1 – bridge – half cell 2
Standard electrode potentials (Eo) :
Example: Zinc – Copper Cell (Daniel Cell)  measurement of spontaneity of the redox
 Zn |Zn2+(1M) || Cu2+(1M) | Cu reaction
 Overall reaction  higher (more positive) Eo = greater driving
o force for the reaction as written, the
 Cathode(+) half – reaction (reduction) greater tendency for it to occur
 Examples: 1.100 V for standard Zn – Cu cell
o and 0.462 V for standard Cu – Ag cell
 Anode (-) half – reaction (oxidation)  Standard Hydrogen Electrode (SHE) –
o arbitrary standard with Eo of 0.0000 V
 Direction of electrons – from anode (-) to o Anode:
cathode (+)
 5% agar of KCl is usually used for the salt o Cathode:
bridge
Sample Problem: Will permanganate ions, MnO4-
Example: Copper - Silver Cell oxidize Fe (II) ions to Fe(III) ions, or will Fe(III) ions
 Cu |Cu2+(1M) || Ag+(1M) | Ag oxidize Mn(II) ions to MnO4- in acidic solution?
Given: MnO4-  Mn2+, Eo = 1.507 V
 Overall reaction
Fe3+  Fe2+, Eo = 0.771 V
o
 Cathode(+) half – reaction (reduction) Solution steps:
o  Choose the appropriate half-reactions from
a table of standard reduction potentials.
 Anode (-) half – reaction (oxidation)
 Write the equation for the half-reaction
o with the more positive E0 value first, along
 Direction of electrons – from anode (-) to with its E0 value.
cathode (+)  Write the equation for the other half-
 5% agar of KCl is usually used for the salt reaction as an oxidation with its oxidation
bridge potential, i.e. reverse the tabulated
reduction half-reaction and change the sign
Insights from comparison of Zinc – Copper cell and of the tabulated E0.
Copper – Silver Cell  Balance the electron transfer. (Do not
 Strength as oxidizing agent multiply the E0 value with the factor used
o Zn2+ < Cu2+ < Ag+ for balancing the equation).
 Strength as reducing agent  Add the reduction and oxidation half-
o Ag < Cu < Zn reactions and their potentials.
Answer to sample problem: Eocell = 0.74 V, MnO4-,
Activity series: permanganate ions will oxidize Fe(II) ions to
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Fe(III) and are reduced to Mn(II) ions in acidic

−
solution.

Nernst equation (for non-standard conditions): −

−
−
−

Relationship of Eocell to Go and K

= potential under condition of interest
= potential under standard conditions
−
= ideal gas constant
= absolute temp in K
−
= # of e- transferred
= 96,487 J/V mol e-
= reaction quotient

for the half – reaction: Sample Problem: Calculate the standard Gibbs free
energy change, G0, at 250C for the following
reaction.
Pb + Cu2+ Pb2+ + Cu

Solution:
Sample Problem: Calculate the initial potential of a
 Eocell is calculated
cell that consists of an Fe3+/Fe2+ electrode in which
[Fe3+]=1.0 x 10-2 M and [Fe2+]=0.1 M connected to a
 is calculated
Sn4+/Sn2+ electrode in which [Sn4+]=1.0 M and
− −
[Sn2+]=0.10 M . A wire and salt bridge complete the
circuit. Temperature is at a standard value of 25 oC.
Some applications of electrochemical cells:
Given: Fe3+ + e-  Fe2+, Eo = 0.771 V
 to determine concentration (e.g. pH meter)
Sn4+ + 2e-  Sn2+, Eo = 0.15 V
– recall Nernst equation
 corrosion (e.g. corrosion of iron)
Solution:
o Anode (oxidation): Fe  Fe2+ + 2e-
 Eocell is calculated
 manifested as pitting
o Cathode (reduction): O2 + 2H2O +
4e-  4OH-
 can be indicated using
phenolphthalein (turns
 Apply Nernst equation pink)
o Cathode (reduction): O2 + 2H2O +
 manifested by the
appearance of rust
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 Corrosion prevention o Maximum work done by the

o plate with less active metal system.
o connect to more active metal o The cell potential if each species in
(sacrificial anode) solution are 0.20M in concentration
o coating and the gases are at 1 atm
o passivation layer (coating that is pressure. (T cell = 298K).
allowed to form naturally) • Draw the cell notation for the cell (Include
o coat with more active metal polarity (sign) and the direction of the
(galvanizing) electron flow.
 batteries (voltaic or galvanic cells) – as it
discharges, its chemicals are consumed 2. Electrolytic cell: A 1.00 M acidified aq. CaCl2
o primary voltaic cells – not solution is electrolyzed using Pt. electrodes at 298K.
rechargeable (e.g. dry cell or A current of 1.50A passes through the solution for
flashlight battery, alkaline cells, 50.0 hours.
mercury battery)  Write the half-reactions at the electrodes.
o secondary voltaic cells – reversible,  What is the decomposition potential, Eocell?
rechargeable (e.g. lead storage / car  Calculate the mass (in grams) of the product
battery, Ni – Cd battery, fuel cells) formed in the cathode.
 What is the ΔGo ?
Maximum useful work, wmax:  Draw a simple schematic diagram of how
 for a voltaic cell, Eocell is (+), ΔG is (-), wmax is the electrolysis setup should look like.
(-)  work done by the system Indicate the electrodes, sign, direction of
o wmax = -nFEocell electron flow, etc.
 for an electrolytic cell Eocell is (-), ΔG is (+), Given:
wmax is (+)  work done on the system O2 (g) + 4H+ + 4e- 2H2O(l) E0= 1.229V
o wmax = nFEoexternal Cl2 (g) + 2e- 2Cl-(aq) E0= 1.360V
Ca2+ (aq) + 4e- 2Ca(s) Eo= -2.870V
Overpotential/Overvoltage  difference between
the actual electrode potential and the
thermodynamic or equilibrium potential
Coordination Compounds
More excercises:
1. Voltaic/galvanic cell: Given the following coordinate covalent bond
standard reduction potentials:  pair of electrons shared from a donor to an
E° (MnO2(s)  Mn2+) = 1.230V acceptor
E°(Cl2Cl-) = 1.360V  usually formed in Lewis acid – base
 Write a balanced (net) cell equation for the reactions
spontaneous reaction.
 Calculate the Example: ammonia (donor) and borontrifluoride
o Standard cell potential, E0cell (acceptor with empty valence orbital)
o Standard Gibbs Free Energy, ΔG° H3N: + BF3  H3N : BF3
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Coordination compound/complexes – metal ion Nomenclature

bonded with ligands
 ligand - Lewis base that coordinates to a  cations first, then anions
central metal atom or ion  ligands in alphabetical number
 donor atom - atom in a ligand that donate a  prefixes used to specify number or each
lone pair of electrons to form a coordinate ligand (di, tri, tetra, penta, hexa, etc.) but
covalent bond prefixes are not included in alphabetization
 unidentate ligand – only one atom can  prefixes that are part of name of ligand (e.g.
serve as donor atom diethylamine) are included in
 polydentate ligand (chelating agent) – has alphabetization
several donor atoms that can coordinate at  if ligands contain the prefixes di, tri, etc. in
the same time their names, the following prefixes are used
 coordination number – number of donor to indicate number: bis, tris, tetrakis,
atoms coordinated to the central atom / ion pentakis, hexakis
 coordination sphere – central atom / ion +  names of most ionic ligands end in –o
ligands coordinated to it  names of most neutral ligands are
unchanged [exceptions: NH3 (ammine), H2O
Example: For the complex compound (aqua), NO (nitrosyl), CO (carbonyl)]
Na3[Co(Cl)6] the coordination number is 6, and the  The oxidation number of a metal that
coordination sphere is 7. The oxidation state of Co exhibits more than one oxidation states is
is 3. designated by a Roman numeral in
parentheses following the name of the
Common monodentate ligands: Fluoro F-, Chloro Cl- complex.
, Bromo Br-, Iodo I-, Azido N3-, Cyano CN-,  If a complex is an anion, the suffix "ate"
Thiocyanato SCN-  (S-bonded), Isothiocyanato ends the name. (e.g. ferrate, plumbate)
NCS- (N-bonded), Hydroxo OH-, Aqua H20,
Carbonyl CO, Thiocarbonyl CS, Nitrosyl NO+, Nitro Examples:
NO2-, Nitrito ONO- O-bonded) 1. Na3[Fe(Cl)6]  sodium hexachloroferrate (III)
2. [Ni(NH3)4(OH2)2](NO3)2 
Other common ligands: Methylisocyanide CH3NC, tetraamminediaquanickel(II) nitrate
Phosphine (phosphane) PR3, Pyridine, Ammine NH3,
Methylamine MeNH2, Amido NH2-, Sulfato SO42-, More practice exercises:
Oxalato C2O4-2
Give the names for the following:
Common chelating ligands: • Ammine, 1. [Cu(NH3)4](NO3)2
methylamine NH3, CH3NH2 (monodentate), 2. (NH4)4[Mn(CN)6]
Ethylenediamine (en) NH2CH2CH2NH2 (bidentate), 3. Na[AlCl4]
diethylenetriamine (dien) NH2CH2CH2NHCH2CH2NH2, 4. [FeBrCl(en)2]Cl
Triethylenetetraamine (trien), 5. [Fe(H2O)4(OH)2]Br
Tetraethylenepentaamine, EDTA

Give the chemical formula for the following:

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• Dichlorobis(ethylenediammine)cobalt(III) Nitrate  coordination isomers – exchange of ligands

• Potassium trioxalatochromate(III) between the coordination spheres of the
• Ammonium cation and anion
diamminetetraisothiocyanochromate(III) o [Pt(NH3)4][PtCl6] and
• Tetraamminedinitroplatinum(IV) bromide [Pt(NH3)4Cl2][PtCl4]
• Tri-aqua-cis-dibromochlorochromium(III)  linkage isomers
o [Co(NH3)5ONO]Cl2 and
Structure of coordination compounds: [Co(NH3)5NO2]Cl2
 determined primarily by coordination
number Stereoisomers
 can be predicted using VSEPR theory (Chem Note: Complexes with only simple ligands can have
16) stereoisomers only if they have coordination
numbers equal to or greater than 4.
Coordination Geometry Metal  geometrical or positional isomers – not
Number Hybridization optical isomers
2 linear sp o cis-trans isomerism
4 tetrahedral sp3 o cis- [Pt(NH3)2Cl2]
4 square planar sp2d or dsp2
5 trigonal dsp3
bipyramidal
5 square d2sp2
pyramidal
6 octahedral d2sp3 or sp3d2 o trans- [Pt(NH3)2Cl2]

Isomerism
 structural/constitutional isomers – same
formula but different ligands
o cis-diammine-cis-diaqua-trans-
 stereoisomers – same ligands but different
dichlorocobalt(III) ions
arrangement

Structural/constitutional isomers:
 ionization or ion-ion exchange isomers
o [Pt(NH3)4Cl2]Br2 (counter ions areBr-
) and [Pt(NH3)4Br2]Cl2 (counter ions  optical isomers/enantiomers  non –
are Cl-) superimposable mirror images
 hydrate isomers – water molecules may be o cis-diammine-cis-diaqua-cis-
changed from inside to outside of dichlorocobalt(III) ion
coordination molecule
o [Fe(OH2)6]Cl3, [Fe(OH2)5Cl]Cl2·H2O,
and [Fe(OH2)4Cl2]Cl2·2H2O
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For octahedral complexes

optical activity - separate equimolar solutions of The five d orbitals are split into:
two optical isomers / enantiomers rotate plane  eg (higher energy) orbitals directed along x,
polarized light by equal angles but in opposite y, and z axes  ,
directions  t2g (lower energy) orbitals directed in
between the axes 
Electronic Spectra  or or  crystal field
 The energy of light absorbed as electrons splitting energy – energy separation
are raised to higher levels is the difference between 2 sets of d orbitals – proportional
in energy between the energy states to crystal field strength of ligands
Valence Bond Theory – uses hybridization concepts
Example: Co(II) – may have 3, 1, or 0 unpaired
electrons

Recall: σ-bonding and π-bonding

Ligands with π-bonding capabilities:
Crystal Field Theory
 ligands with occupied p-orbitals are
 Bonding between the metal and the ligands
potential π-donors
is considered to be largely electrostatic and
 ligands with vacant d orbitals are potential
thus the energy of the metal ion and
coordinated ligands is lower than that of π-acceptors
isolated ions because of electrostatic
Crystal field strength for some common ligands:
attraction.
I- < Br- < Cl- < F-, OH-, <H2O < NCS- < NH3 < en < NO3-
 Ligands are treated as point charges and
<CO, CN
the effect of these point charges are
considered on the relative energies of the d  weak field, high spin  π-donors, interact
strongly with metal orbitals, large crystal
orbitals.
field splitiing, large
 The energies of the metal d-electrons are
 strong field, low spin  π-acceptors,
increased by the repulsive interaction
between them and the electrons from the interact weakly with metal orbital, small
ligands  give rise to the splitting of the crystal field splitting, small
metal d-orbitals
spectrochemical series  colors of complexes,
reflects the ligand arrangement based on crystal
field strength
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High spin complexes (w/ weak field ligand):

Recall: Paramagnetism
paramagnetic  w/ unpaired electrons
Low spin complexes (w/ strong field ligand): diamagnetic  w/out unpaired electrons

The visible range spectra  is of the same

order of magnitude as the energy of the photon of
visible light  absorbs light that excites e- from
lower energy d orbitals to higher energy d orbitals

 spectral color  color or wavelength of

light absorbed
 complementary color  color or
Complexes with both strong field and weak field wavelength of light transmitted
ligands:
Example:
[Cr(H2O)6]3+(light violet)  weak field ligand, small
, absorbs lower energy/larger wavelength light
(ROY end), transmits higher energy/smaller
wavelength light (BLUE end)
[Cr(NH3)6]3+ (yellow)  strong field ligand, large
, absorbs higher energy/smaller wavelength
light (BLUE end), transmits lower energy/larger
wavelength light (ROY end)

Consider the complex [FeX6]4- For tetrahedral complexes  splitting is opposite

If X = Cl- (weak field ligand)high spin complex of that of octahedral

Notes: (1) is about 4/9 of (2) all

tetrahedral complexes are paramagnetic
For square planar complexes
If X = CN- (strong field ligand)  low spin complex
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 d8 central metal
 almost always low spin (diamagnetic)
 example: heavy metals (46Pd2+, 78Pt2, 77Ir+
and 79Au3+)

Comparison:

Limitation of CFT: fails to consider the actual

covalent character formed between the metal and
the ligands

Practice Exercise: K4[MnF6]

 Name : potassium hexafluoromanganate (II)
 Coordination sphere = 7
 Coordination number = 6, Octahedral
geometry
 Mn+2 d5 (Mn=25)
 F is a weak field, therefore, a high spin
complex is formed where the e- will occupy
eg orbitals before pairing in the t2g
 Paramagnetic.
 We expect the complex to absorbed in the
red-orange region and hence, the
compound would likely appear green to
blue.