CHM2280

SYLLABUS

WINTER2015

GeneralChemistryII

Professor C. F. Poole,
185 Chemistry
046DeroyMW4:305.50

Martin Luther King Holiday 1-19

Spring Break 03-16 to 03-21
First Class, Monday 01-12
Last Class, Monday 04-27

Course Texts
Recommended
Quantitative Chemical Analysis, 8 th Edition,
Daniel C. Harris, Freeman, 2010
(e-book version available from Sapling)
Optional

Solution manual for Quantitative Chemical

Analysis is available
Online Homework

You will need to register with Sapling Learning

COURSEOUTLINE
Module 1 Introduction to Measurement Science
Module 2 Chemical Equilibria
Module 3

Acid-Base Chemistry and Titration

Module 4

Compleximetric (EDTA) Titrations

Module 5

Fundamentals of Electrochemistry and Redox

Titrations
Module 6

Fundamentals of Spectroscopy

Module 7

Atomic Spectroscopy

Module 8

Fundamentals of Separations

GRADING
3PeriodicExamsworth200pointseach =600
ComprehensiveFinalExamination =400
Homework(10bestscores)
=200
Total =1200
.

Nomakeupexamsandnoexamcanbedropped.

Typicalgradescaleforthisclass:
A,A
85100%
B+,B,B 8459
C+,C,C 5836
D+,D
3526
F 025
Thisisnotagradingguarantee.GradingscaleusedforFall2013andshouldbeareasonableguide

EXAM SCHEDULE: Tentative and subject to change with adequate

notice 02-09 (M), 03-12 (W), and 04-22 (W). The final examination is
04-29 (W) from 4:30-7:00. All exams will be in 046 Deroy unless
indicated otherwise.

General Chemistry II
Module 1
Introduction to Measurement
Science

Goals of Chemical Analysis

Determine the composition of
Samples
Identification of components (Qualitative
Analysis)
Relative composition (Quantitative
Analysis)

Different approaches for atoms and

molecules
Elemental composition (Atoms)
Structural elucidation (molecules)

General Approaches
Classical Methods (wet chemistry)
Isolation by precipitation, extraction, distillation, etc.
Identification by converting to products identified from
similarity of physical properties to a known standard
Quantification by gravimetric or volumetric methods

Instrumental Methods
Isolation by chromatographic methods
Identification by spectrophotometry
Quantification by physicochemical methods using
special purpose instruments

Classical Methods
Semimicro Qualitative Analysis
Identification of ions by color formation,
precipitation, gas production, selective solvation
Visual detection of changes

Gravimetric Analysis
Formation of sparingly soluble salts (precipitates)
Quantitative analysis based on weight

Titrimetric Analysis
Neutralization (acid vs base)
Precipitation (insoluble salt formation)
Complex formation
Redox reactions

Instrumental Methods
Interaction of Electromagnetic Radiation
with Matter (Spectroscopy)
Electrochemistry
Mass Spectrometry
Thermal Methods
Vacuum Spectroscopy (surface analysis)
Sensors
Separation Methods

Analytical Workflow
Collection of a Representative Sample
Sample Preparation
Isolation
Concentration
Matrix Simplification

Chemical Analysis
Classical methods
Instrumental methods

Data Analysis

Scientific Units

Length
meter m
Mass
kilogram kg
Amount of substance mole (mol) M
Time
second s
Temperature
kelvin K
( 273.16+C)

Electric current

ampere A

Derived Scientific Units

Frequency
hertz
Hzs-1
Force
newton N m.kg.s-2
Pressure
pascal
Pa kg.m-1.s-2
Energy
joule J m2.kg.s-2
Electrical charge
Coulomb C A.s-1
Electrical potential Volt
V m2.kg.A-1.s-2

Scientific Notation
Consists of a number and a scale
factor based on powers of 10
1.23 x 10n
Common non-numeric abbreviations
tera
giga
mega
kilo k
deca

T a = 1012 pico p a = 10-12

G a = 109
nano n a = 10-9
M a = 106
micro
a = 10-6
a = 103
milli m a = 10-3
da
a = 10
centi c a = 10-2
deci d a = 10-1

Solutions
A solution is a homogeneous mixture of two
or more substances
Major component: the solvent
Minor components: the solutes
The concentration of the solute(s) is the amount
of solute contained in a specified volume (mass)
of solution (solvent)
Molarity (M) = the number of moles of a solute per liter
of solution.
Concentrations are generally designated in terms of
molarity [C]

Chemical Concentrations
The atomic weight of an element is the
weight in grams of 1 mole of atoms
Molecular Weight = (atomic weights of all atoms)
MW is the weight in grams of 1 mol of molecules
MW of HCl = AW of H + AW of Cl = 1 + 35.5 =
36.5 g
1 mol of HCl weighs 36.5 g
1 mol solution of [HCl] contains 36.5 g HCl in 1
liter of solvent

Ionic Solutions
An electrolyte is a substance that
dissociates into ions in solution.
Strong electrolytes are mostly
dissociated in solution NaCl Na+ + Cl Weak electrolytes are mostly
undissociated in solution

Ionic Solutions
The molecular weight of a strong
electrolyte is
called the formula weight (FW) because it
is the
(AW of the atoms in the formula), even
though there are very few molecules with
that formula present in solution
FW (or F) of NaCl = 22.99 + 35.45 = 58.44
[NaCl] = 58.44 g of NaCl in 1 L of solution

Molality
Molality (m) is the number of
moles of a substance per
kilogram of solvent (not total
solution)
Molality is independent of
temperature
Molarity depends upon temperature
because the solution volume

Relative Composition

For very small quantities parts per million (ppm) and part
Billion (ppb) are used
1 ppm = 1 g of substance per 106 g of total solution
1 ppb = 1 g of substance per 109 g of total solution
For gases. Volume is used instead of mass

To prepare a solution with a desired

molarity
Calculate the correct mass of
To prepare
solute needed (molecular weight x
solutions
volume in L)
with a d
Weigh out the correct mass of the
solute.
Dissolve solute in solvent so that
the total volume after mixing is
the desired volume.
Dilute solutions can be prepared
from concentrated solutions.

Example Calculation
The molarity of concentrated HCl is 12.1
M. How many mililiters of this reagent
should be diluted to 1.000 liters to make
0.100M HCl
Mconc = 12.1
Vconc = x
Mdil = 0.100
Vdil = 1000
x = (0.100 M) x (1000 ml) =
8.26 ml
(12.1 M)

Stoichiometry
The calculation of quantities of
substances involved in a
chemical reaction
Mater can neither be created nor
destroyed
(all reactant atoms) = (all product
atoms)
Electrical neutrality is conserved
(all reactant charges) = (all product
charges)

How many Tablets Should We

Analyze?

Each tablet contains 15 mg of iron

How many tablets should we analyze to provide 0.25 g
of Fe2O3?
How many g of Fe are in 0.25 g of Fe2O3
First calculate the moles of Fe2O3 (x) in 0.25 g
x = 0.25/159.69 = 1.6 x 10-3 moles
1 mol Fe2O3 =
159.69 g
Since 1 mol of Fe2O3 contains 2 moles of Fe
2x = 2 x 1.5 x 10-3 = 3.2 x 10-3 moles
Convert to g of Fe
= 3.2 x 10-3 x 58.845 = 0.18 g Fe

1 mol Fe =

Significant Figures
Those digits in a number which are
known with certainty plus the first
uncertain digit

Significant Figures
Only significant figures should be used
in recording a result
Balance 1.234 5 g
Burette 1.23 ml
When not stated explicitly uncertainty
is 1
Otherwise always stated 5.34 0.04
(unit)

Particular Problem with

Zeros
Zeros which appear between other digits
are always significant
Initial zeros are never significant (only
indicate the position of the decimal point)
0.0724 g of 72.4 mg (3 significant figures)
Exception: initial zeros to the right of the
decimal point in logs are significant
0.079 is the log 1.20 (3 significant figures)
Terminal zeros are generally considered significant
30,200 (5 significant figures)

Particular Problem with

Zeros
Terminal zeros in a number without a
decimal point may or may not be
significant
900 cm may have 1, 2 or 3 significant figures
900. cm has three significant figures

Uncertainty can be removed through the

use of scientific notation
9.0 x 102 has two significant figures
9 x 102 has one significant figure
9 x 106 has one significant figure

Significant Figures
Addition and Subtraction
1.362 x 10-4 5.345 7.26 x 1014
+ 3.111 x 10-4 + 6.728
- 6.69 x 1014
4.473 x 10-4
12.073
0.57 x 1014
Number of digits = Number of significant
figures
This number can be greater or less than the
number of significant figures in the original
data

Significant Figures
Addition and Subtraction
For numbers with different numbers of
digits the result is governed by the
number with the fewest digits
Molecular weight of KF2
18.998 4032 (F)
18.998 4032 (F)
83.798
(Kr)
121.794 8064 (not significant)

Significant Figures
Addition and Subtraction
scientific notation: express the
numbers with the same exponent
1.632 x 105 + 4.107 x 103 + 0.984 x 106
1.632 x 105
+ 0.04107 x 105
+ 9.84 x 105
11.51 x 105 1.151 x 106

Significant Figures
Rounding numbers to obtain the correct
number of digits
When the first insignificant digit is 5
round last significant digit up by +1
When the first insignificant digit is < 5
leave the last significant digit
unchanged (round number down)
1.794 846 to four significant figures 1.795
1.794846 to five significant figures 1.7948

Significant Figures
Multiplication and Division
Limited to the number of digits contained
in the number with the fewest significant
figures
The number of digits retained is
independent of the power for
exponentials
3.26 x 10-5 4.3179 x 1012
34.60
x 1.78
x 3.6
x 10-19
2.46287
5.80 x 10-5 1.6
x 10-7
14.05

Significant Figures
Logarithms and Antilogarithms
n is the antilogarithm of a
Logarithm has a characteristic and a mantissa
Log 339 = 2.530
Characteristic = 2 (integer
part)
Mantissa = 530 (decimal part)
logarithm to number
Number of digits in the mantissa = number of
significant figures
logarithm to antilogarithm

Significant Figures
Logarithms and Antilogarithms
log 0.001237 = -2.9076
log 1237 = 3.0924
log 3.2 = 0.51
antilog 4.37 = 2.3 x 104
104.37 = 2.3 x 104

Sources of Errors
Gross errors
Mistakes (transcription errors, missing reagent, etc)
Recognized by outlier tests

Systematic errors
Cause all results to be in error in the same sense (same sign
and magnitude)
May go undetected unless a true value is known
Accuracy effected without loss of precision

Random errors
Individual results fall on both sides of the average value
Vary in sign and magnitude and are unpredictable
Average out and approach zero with sufficient measurements
Precision affected without loss of accuracy

Accuracy
Accuracy is an indication of the
closeness of a measurement to the
true value for the sample
Determined by the absolute error or
relative error
the sum of the contribution of
systematic and random errors to the
measurement
Gross errors also affect accuracy but
results known to contain gross errors are
not used for analytical measurements

Bias (Systematic Error)

Precision
The closeness of a set of results to each other
With sufficient replication of a measurement
the contribution of random errors can be
removed
Random errors have different signs and
magnitudes but their sum tends to zero as the
number of measurements increases
Random errors in experimental measurements can
often be described by a Gaussian model

No number of replications can account for

systematic errors

Gaussian Distribution

Gaussian Model
Measure of Central
Tendency
(Average of all values)
An indication of the true
Measure
value of the spread of the results
(Standard deviation of all values)
An indication of the precision of the
measurements

Accuracy and Precision are

Independent Quantities

Uncertainty is a property of all

measurements
The uncertainty of a result is a parameter that
describes a range within which the values of
the quantities being measured is expected to
lie, taking into account all sources of error
Uncertainty is associated with all individual steps
of an analytical procedure and an accumulated
uncertainty with a single measurement
Uncertainty is sum of method errors
Gross errors (must be identified and rejected)
Systematic errors (bias)
Random errors

Problem Highlight
Measurement uncertainty must be expressed as
a single numerical value
Sources of errors
errors of method
instrument errors
personal errors
It contains two types of contributions
Bias errors = xi -
Random errors = standard deviation
Not a true value (estimate)
Not independent of the measurements made

Absolute and Relative

Uncertainty

Absolute uncertainty = uncertainty associated

with a measurement ( error)
For a single measurement it is the experimental
uncertainty for that measurement
0.02 ml in reading a burette
0.0001 g in weighing a sample
Relative uncertainty
scales the
absolute uncertainty to
the
quantity measured
Sometimes expressed as
a percentage

(or 0.2
%)

Combining Individual
Uncertainties
Addition or subtraction of random errors
( y = x1 + x2) or ( y = x1 - x2)
v = (e12 + e22)

Multiplication or division of random

errors
( y = x1.x2) or ( y = x1/x2)
%v = (%e12 + %e22)
%e = percent relative error (100ei/xi)
Absolute uncertainty in v = %e.x

Propagation of Uncertainty from

Random Errors
Addition and
Subtraction
e4 = [(0.03)2 + (0.02)2 +
(0.02)2]
e4 = 0.04
3.06 0.04 (absolute
uncertainty)
(0.04/3.06 x 100) = 1%
3.06 1% (relative

Propagation of Uncertainty from

Random Errors
Multiplication and Division
First convert all uncertainties to
percent relative uncertainty and
proceed as for subtraction and addition

Combining Individual
Uncertainties
Addition or subtraction of systematic
errors
( y = x1 + x2) or ( y = x1 - x2)
y = (1 + 2) with retention of sign

Multiplication or division of
systematic errors
( y = x1.x2) or ( y = x1/x2)
y = (1/x1 + 2/x2) with retention of sign

Combining Uncertainties from

Systematic and random Errors
The usual method of tackling
systematic errors is to treat them as
coming from a rectangular
distribution
Contribution to standard uncertainty is
obtained by dividing the error by 3
Combine uncertainty from systematic
errors (/3) as if it came from a source
of random error