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ELEMENTARY QUANTITATIVE ANALYSIS

CHEM 221
 ELEMENTARY QUANTITATIVE ANALYSIS
CHEM 221, Fall 2007
Tues & Thur 9:30-10:45, Rm. 112 Hamilton Hall

COURSE OUTLINE

Instructor: Dr. Robert Powers

Office Labs
Address: 722 HaH 720-721 HaH
Phone: 472-3039 472-5316
e-mail:rpowers3@unl.edu
web page: http://bionmr-c1.unl.edu/

Office Hours: 10:30-11:30 am MWF or by Special Appointment

I am in my office many other times during the week and am always
willing to speak with you if you find me in or make an appointment.

Teaching Assistants:
Ms. Jennifer Copeland phone: 472-5316 office: 721 HaH
Ms. Kelly Mercier phone: 472-5316 office: 721 HaH
Mr. Rob Waters contact: Resource center e-mail: bor9455@hotmail.com
 COURSE OUTLINE
Required Items:
(i) Chem. 110 is the only prerequisite
(ii) Text: "Quantitative Analysis" 7/e Daniel C. Harris, Freeman & Co., New York
(iii) Lab Manual: "Laboratory Manual for Quantitative Chemical Analysis", J.D.Carr (2007)
(iv) Laboratory Notebook: bound (not spiral), use one with grids instead of lined pages for
graphs.
(vi) Black Sharpie for labeling glassware
(vii) Calculator for exams and lab (TI-89 style or a simpler model)
(viii) Laptop (optional) to run Excel calculations during lab

Course Work:
Exam 1: 100 pts (Thurs., Sept. 20)
Exam 2: 100 pts (Thurs., Oct. 18)
Exam 3: 100 pts (Tues., Nov. 20)
Final: 200 pts (10am-12pm, Wednesday, Dec. 19)
Laboratory: 400 pts (due at end of each lab)
Lab Notebook: 100 pts (due at end of semester)
Total: 1000 pts

Homework problem sets will not be collected or graded, but will aid
your preparation for the exams.
 Lecture Topics
Date Chapter Topic Problems
Aug 28 Chap 0 & 1 Measurement 0-1,5-A,6 & 1-5,7,22,24,26
Aug 30 Chap 2 & 3 Tools 2-D,1,10,15, & 3-A,5,9,11
Sept 4 Chap 3 Error 3-12,13,15,18,21,23
Sept 6 Chap 27 Gravimetry 27-2,3,7,14,18,25,26
Sept 11 Chap 4 Statistics 4-B,E,2,3,6
Sept 13 Chap 4 Statistics (cont) 4-9,11,13,14,15,18,22
Sept 18 Chap 5 Calibration 5-A,B,C,22,23
Sept 20 EXAM 1
Sept 25 Chap 6 Equilibrium (Intro) 6-A,B,G,I,K,1,2,3,5,13
Sept 27 Chap 6 Equilibrium (cont) 6-17,21,37,40,54
Oct 2 Chap 7 Titrations 7-B,C,D,1,2,4,8,11,13
Oct 4 Chap 8 Activity 8-A,C,1,4,8,14
Oct 9 Chap 8 Equilibrium (systematic) 8-F,G, H,10,16
Oct 11 Chap 8 Equilibrium (more) 8-18,8-21,8-23
Oct 16 Chap 8 Equilibrium (even more) 8-26, 28
Oct 18 EXAM 2
Oct 22-23 Fall Break
Oct 25 Chap 9 Monoprotic acid/base 9-B,C,G,H,4,6,10,13,19
Oct 30 Chap 9 Monoprotic (again) 9-24,26,27,29,30,36,37
Nov 1 Chap 10 Polyprotic acid/base 10-A,1,2,4,7,9,16,23,29,31,33,38
Nov 6 Chap 11 Acid/base Titrations 11-A,B,F,G,I,3,5,6,7,13,16
Nov 8 Chap 11 Acid/base Titrations (cont) 11-23,27,34,36,45,46,54,64
Nov 13 Chap 12 EDTA Titrations 12-B,2,4,5,6,13,22,28
Nov 15 Chap 14 Electrochemistry 14-B,D,I,2,3,15,18,25,41
Nov 20 EXAM 3
Nov 22-23 Thanksgiving
Nov 27 Chap 15 Potentiometry 15-E,6,7,8,10,13,17,23,24
Nov 29 Chap 16 Redox Titrations 16-A,C,1,2,7,14,15,16,24
Dec 4 Chap 18 Spectrophotometry 18-A,C,D,1,6,8,16,18,19
Dec 6 Chap 23 Separations 23-B,1,2,3,29, 44
Dec 11 Chap 23 Separations
Dec 13 Chap 24 Gas Chromatography 24-A,B,C
Dec 19 FINAL EXAM 10:00-12:00
 Tentative Lab Schedule
Date Experiment Value
Aug 27-31 Check-in, Safety, Introduction to Analytical Chemistry 0
Sep 4-7 Statistics (Exp 2) 50
Sep 10-14 Gravimetric Aluminum (Exp 3) 150
Sep 17-21 Gravimetric Aluminum (cont)
Sep 24-28 Volumetric Soda Ash (Exp 4) 200
Oct 1-5 Volumetric Soda Ash (cont)
Oct 8-12 Titration of Weak Acid & pK Determination (Exp 5) 100
Oct 15-19 Complexometric Titration for Water Hardness (Exp 6) 100
Oct 24-30 Potentiometric Titration of Iron (Exp 7 ) 100
Oct 31-Nov 6 Coulometric Analysis of Vitamin C (Exp 14 ) 100
Nov 7 13 Spectrophotometric Determination of Chromium and Cobalt (Exp 10 ) 100
Nov 14-21 Spectrophotometric Determination of Iron (Exp 11 ) 100
Nov 26-30 Gas chromatography of Aromatic Hydrocarbons (Exp 15 ) 100
Dec 3-7 Lab Make-up
Dec 10-14 Check out of lab
TOTAL 1100
Due to equipment limitations, experiments # 7, 10, 11, 14 & 15 will
Scaled to 400 for final grade
be taken in different order by portions of the students.

NOTE: Students having a Monday lab should make up Sept 4 lab on Sept 7 (Friday)
 COURSE OUTLINE
Lectures:

ALL PowerPoint lecture notes are available online on BlackBoard and my web-
site (http://bionmr-c1.unl.edu/).

!!!!The Lectures Notes Are Not Meant To Replace Attending Class!!!!!

Laboratory:

50% of your grade in CHEM 221 is based on your laboratory effort.

You will be furnished samples whose composition is unknown to you.

You will be asked to determine how much of a given analyte is present.

You will be graded on how well you agree with the correct answer.
You are allowed to re-do one lab during the next to last week
You are allowed to re-submit one lab calculation if you made a math mistake at no

penalty to your lab grade:

you must clearly state what the mistake was and how you corrected it
each subsequent resubmission of a calculation error will incur a progressive 10% penalty

2nd re-submission -10%, 3 rd re-submission -20%, 4 th re-submission -30%

You will also be graded on how well you keep and maintain your lab notebook.

Good Lab Practice and Techniques are Essential

 Lab Notebook Techniques
The Lab Notebook Must:
State what was done.
State what was observed
Be understandable to someone else

Include Complete Description of Experiment:

Purpose
Methods
Results
Conclusions

Include Balanced Chemical Equations for Every Reaction Used

Paste Hardcopies of Important Data in Notebook

Include locations Where other Data is stored (computer files)

Notebooks are Legal Documents and Routinely Used for Patent

Litigation

Laboratory Notebook should be bound (not spiral), use one with grids
instead of lined pages for graphs.
 Lab Notebook Techniques

This Notebook Page is

incomplete and a Useless
Document. Limited Detail.

This Notebook Page Has

Precise Description with
Adequate Detail
 How to Read and Use a Buret

When reading a buret, it is important

that your line of sight be in a direction
perpendicular to the buret column.

All buret reading should be done

using a buret card.
 How to Read and Use a Buret

Upper limit of the black streak ought to

be placed just under the meniscus, so
that the bottom of the meniscus can be
seen distinctly against a narrow zone
of white.

Read volume associated with bottom of

meniscus.
A 50 mL buret can be read to 0.01 ml.
A constant dark reflection
against a white background
enables higher precision in
determining relative titrant
volumes.
 How to Read and Use a Buret

A bubble in the nozzle of a buret will

produce an inaccurate volume reading
if the bubble escapes during a titration

The quickest way to get rid of bubbles

is to fill the buret with titrant and open
the valve.

Some bubbles may require light

tapping to dislodge them.
Microsoft Excel Demo
 Introduction to Analytical Chemistry

Identifying an Unknown Is Not As

Easy as Portrayed by the CSI TV
Show.

Typically Requires More Than One

Experiment and > 45 Minutes of
Analysis with corresponding high
cost (single DNA analysis ~$10,000)

CSI: Crime Scene Investigation

 Introduction to Analytical Chemistry
Background

1.) Definition:

ANALYTICAL CHEMISTRY: The Science of Chemical Measurements.

2.) Types of Questions Asked in Analytical Chemistry

a.) What is in the sample? (qualitative analysis)
b.) How much is in the sample? (quantitative analysis)

3.) Techniques used in Analytical Chemistry:

a.) Wet Chemical Methods: titrations, color-forming reactions,
precipitations, etc.
b.) Instrumental Methods: spectrometry, chromatography, etc.

What is it ?
How much is there?
How pure is it?
What are the impurities?
 Introduction to Analytical Chemistry
The Analytical Process

1.) Formulating the Question:

Translate General Question into Specific Question

Is this water safe to Drink? What is the concentration of Arsenic in the water sample?

2.) Selecting Analytical Procedures:

Source Caffeine Serving
a.) Choose procedure to measure Arsenic in water (mgs per size (oz)
(i) Uncertainty in measurement serving
(ii) Limit of detection Regular coffee 106-164 5
(iii) Destroy sample Decaffeinated 2-5 5
(iv) Availability, time, cost coffee
b.) If necessary, develop new procedure Tea 21-50 5
Cocoa beverage 2-8 6
3.) Sampling: Baking 35 1
a.) Select representative material to analyze chocolate
(i) dont use the entire sample Sweet chocolate 20 1
(ii) consistency in sample collection Milk chocolate 6 1
soft drinks 36-57 12
 Introduction to Analytical Chemistry
The Analytical Process

4.) Sample Preparation:

a.) convert sample into form suitable for chemical analysis
(i) Dissolve sample
(ii) Concentrate sample

(iii) Remove species that interfere with analysis

 Introduction to Analytical Chemistry
The Analytical Process

4.) Sample Preparation:

a.) Example:

How do you prepare samples for Drug Discovery?

What we want to know:
Is the drug active? Does it cure the disease/illness?
How is the drug taken? (Pill, injection)
How often does the drug need to be taken?
Does the drug have side-effects?

How these Questions are Typically Addressed:

Treat animal (rat, mice, etc) with drug
Monitor drug duration in animal
Monitor location of drug accumulation
Monitor animal health
Tumor size is measured by fluorescence
How do you treat the animal with the drug? through the mouse skin using quantum
How do you monitor the drug concentration in the dots as a function drug dosage
Animal?
How do you determine the drug location?
How do you determine the animals health?
M. Dahan et al., Science (2003) 302:442-445
 Introduction to Analytical Chemistry
The Analytical Process

4.) Sample Preparation:

a.) Example:

How do you prepare samples for Drug Discovery? Cross-section of sacrificed

mouse showing tissue
removal
Inject mouse with
drug

Tissue plug from

mouse kidney

Determine drug quantity and distribution

Chromatography indicates presence of
drug an metabolites in tissue sample Regulatory Toxicology and Pharmacology 31, S57S62 (2000)
 Introduction to Analytical Chemistry
The Analytical Process

5.) Analysis:
a.) measure concentration of analyte in several identical
aliquots (portions)
(i) Replicate measurements uncertainty in the
analysis
Avoid large errors
Reliability of measurement
(ii) Calibration Curve
Measure response for known samples

6.) Report and Interpretation of Results

7.) Drawing Conclusions
a) How the Report is used
 Units and Concentrations
To a large extent, analytical chemistry is a science of measurement
and measurements require minimizing errors

Quantity Unit (Symbol)

Length Meter (m)
Mass Kilogram (kg)
Time Second (s)
Units of Measurement Electric current Ampere (A)
Temperature Kelvin (K)
1.) SI Units: Luminous Candela (cd)
a.) international units of measurement (metric units) intensity

b.) ALL SI units are based on certain fundamental Amount of Mole (mol)
substance
quantities
Plane angle Radian (rad)
Solid angle Steradian (sr)
Units and Concentrations
Units of Measurement
Standards of length were once represented by the distance between two
marks on a solid metal bar. Copies of these standards were displayed in
public places so that people could check the accuracy of the rules they
were using.

Standards Of Length (1876) Trafalgar Square

In 1588, Elizabeth I issued a new standard yard which remained

the legal British yard for over 300 years.
 Units and Concentrations
Units of Measurement
History of the meter
Origins of the meter go back to at least the 18th century
Two competing approaches to the definition of a standard unit of length.
define the meter as the length of a pendulum having a half-period of one second

define the meter as one ten-millionth of the length of the earth's meridian along a

quadrant

(1791) French Academy of Sciences chose the meridian

force of gravity varies slightly over the surface of the earth, affecting the period of the

pendulum.
meter equal 10-7 of the length of the meridian through Paris from pole to the equator.

prototype was short by 0.2 millimeters because researchers miscalculated the

flattening
of the earth due to its rotation.

(1960) used a definition based upon a wavelength

of krypton-86 radiation

(1983) meter replaced by the following definition:

The meter is the length of the path traveled

by light in vacuum during a time interval of

1/299 792 458 of a second.

International Prototype Meter standard bar made of platinum-iridium

Units and Concentrations
Units of Measurement

The Saga of Claude mile Jean-Baptiste Litre

International System of Units uses the character "l" (lower-case L) to denote the
metric unit of volume litre (liter).
It is often difficult to distinguish between the character "l" and the digit "1" in
certain fonts or when handwritten. 1 liter
International System of Units only permits the use of a capital letter when the

unit is named after a person.

Kenneth Woolner of the University of Waterloo perpetuated a hoax in

the April 1978 issue of CHEM 13 News
Woolner created the fictional character of Claude mile Jean-Baptiste Litre
with a distinguished scientific career where he purportedly proposed a unit of
volume measurement.

since no such person existed for "L", it seemed reasonable that one should be invented. Reg
suggested that I should write a "biography" for the April issue of CHEM 13 NEWS, and over the
course of an evening (which included, I think I recall, most of a bottle of scotch) we generated
much of the substance of an 18th century life, full of drama, revolution and romance.
Dr. Woolner , 1988
 Units and Concentrations
Prefix Symbol Factor
Units of Measurement Mega M 106
Kilo k 103
1.) SI Units: Hecto h 102
d.) To indicate multiples or fractions of units, various Deca da 101
prefixes are used
Deci d 10-1
Centi c 10-2
Milli m 10-3
Micro 10-6
Nano n 10-9
Example: Pico p 10-12
3.2x10-11 s = 32 x10-12 s = 32 ps Femto f 10-15
Atto a 10-18
 Units and Concentrations
Quantity Unit Symbol SI equivalent
Units of Measurement Volume liter L *10-3 m3
milliliter mL *10-6 m3
1.) SI Units: Length angstrom *10-10 m
e.) conversions to SI units
inch In. *0.0254 m
f.) Liter is commonly used for
Mass pound lb *0.45359237 kg
volume instead of m3
metric ton *1000 kg
Force dyne dyn *10-5 N
Pressure bar bar *105 Pa
atmosphere atm *101325 Pa
torr Torr 133.322 Pa
pound/in2 psi 6894.76 Pa
Energy erg erg *10-7 J
electron volt eV 1.602176462x10-19 J
calorie, thermochemical cal *4.184 J
Calorie (British) Cal *1000 cal = 4.184 kJ
British thermal unit Btu 1055.06 J
Power horsepower 745.700 W
Temperature Centigrade (= Celsius) C
o
*K - 273.15
Fahrenheit F
o
*1.8(K 273.15) + 32
 Units and Concentrations
Units of Measurement

2.) Expressions of Concentration:

a.) Molarity (moles/L, or M):
(i) Most common unit of concentration
Gives number of moles of a substance in 1 liter of the given solvent.
Recall: 1 mole (mol) of a substance = 6.022 x 10 23 units (atoms, molecules,
ions, etc).
Molecular weight (MW): the mass of a substance that contains 1 mole.
Example:

Find the concentration in Molarity (M) of 12.00g of benzene (C 6H6) dissolved up

to a total volume of 250.00 ml in hexane.

MW benzene = 6 * (12.011) + 6 * (1.008) = 78.114 g/mol

No. Cs at. wt. C No. Hs at. wt. H

1mol
Conc. C6H6 = (12.00g)( ) = 0.6144 M
78.114g
0.2500L
Make Sure Units Cancel!
 Units and Concentrations
Units of Measurement

2.) Expressions of Concentration:

b.) Formality (F):
(i) Concentrations expressed in M describe the actual concentration of a given
chemical species in solution.

(ii) Some chemicals when placed in solution will dissociate or converted to

multiple forms
Example:

Acetic Acid:
(iii) Not convenient to refer to the concentrations of each individual form.
(iv) Instead, concentration of total substance originally added to the solution is
used.
Formal concentration or Formality given in (mol/L)
Note: For compounds with a single form in solution, M = F
 Units and Concentrations
Units of Measurement

2.) Expressions of Concentration:

b.) Percent Composition:
(i) Weight Percent (wt/wt or w/w): Concentration expressed in terms of mass of
substance versus the total mass of the sample.

mass of subs tan ce

Weight percent x ( 100 )
mass of total solution or total sample

(ii) Volume Percent (vol/vol or v/v): Concentration expressed in terms of volume of

substance versus the total volume of the sample.

volume of subs tan ce

Volume percent x( 100 )
volume of total solution or total sample

(iii) Weight-Volume Percent (wt/vol or w/v): Concentration expressed in terms of

mass of substance versus the total volume of the sample.

mass of subs tan ce

weight volume percent x ( 100 )
volume of total solution or total sample
 Units and Concentrations
Units of Measurement

2.) Expressions of Concentration:

b.) Percent Composition:
(iv) Instead of expressing concentrations as a percentage, express in terms of:

parts per thousand (ppt) x103
parts per million (ppm) x106

Parts per billion (ppb) x109

3.) Solution Preparation:

a.) Dilution of a Solution:

McVc = MdVd

where:
Mc = Molarity of substance in the concentrated solution
Vc = volume of concentrated solution used
Md = desired Molarity of the diluted solution
V = total volume of final diluted solution
 Units and Concentrations
Examples

How many grams of perchloric acid, HClO4, are contained in 37.6 g of

70.5 wt% aqueous perchloric acid? How many grams of water are in
the same solution?
 Units and Concentrations
Examples

What is the maximum volume of 0.25M sodium hypochlorite solution

(NaOCl, laundry bleach) that can be prepared by dilution of 1.00 L of
0.80 M NaOCl?