Ch.

1: Chemical Measurements

Outline:

• 1-1 SI Units

• 1-2 Concentrations in Chemistry

• 1-3 Preparing Solutions

• 1-4 Stoichiometry & Gravimetric Analysis

• 1-5 Introduction to Titrations

• 1-6 Titration Calculations

 Scale of Measurements
The possible scale of measurements in analytical chemistry is astounding, ranging from
the atomic level to the size of galaxies!
An electrode with a tip smaller than a single cell allows us to measure neurotransmitter molecules released by a nerve cell in response
to a chemical stimulus. Neurotransmitter molecules released from one vesicle (a small compartment) of a nerve cell diffuse to the
electrode, where they donate or accept electrons, thereby generating an electric current measured in picoamperes (10−12 amperes) for
a period of milliseconds (10−3 seconds).

(a) Carbon-fiber electrode with a 100-nanometer-diameter (100 × 10−9 meter) tip extending from glass capillary. The
marker bar is 200 micrometers (200 × 10−6 meter). [From W.-H. Huang, D.-W. Pang, H. Tong, Z.-L. Wang, and J.-K.
Cheng, Anal. Chem. 2001, 73, 1048.] (b) Electrode positioned adjacent to a cell detects release of the neurotransmitter,
dopamine, from the cell. A nearby, larger counterelectrode is not shown. (c) Bursts of electric current detected when
dopamine is released. Insets are enlargements. [From W.-Z. Wu, W.-H. Huang, W. Wang, Z.-L. Wang, J.-K. Cheng, T. Xu, R.-
Y. Zhang,Y. Chen, and J. Liu, J. Am. Chem. Soc. 2005, 127, 8914.]
SI Units
SI Derived Units
Unit prefixes
Converting between units
 Careful with your units! *
In 1999, the $125 million Mars Climate Orbiter
spacecraft was lost when it entered the Martian
atmosphere 100 km lower than planned.

The navigation error would have been avoided if

people had written their units of measurement.
Engineers who built the spacecraft calculated
thrust in the English unit, pounds of force. Jet
Propulsion Laboratory engineers thought they
were receiving the information in the metric unit,
Newtons.

Nobody caught the error.

The spacecraft was meant to enter an orbit 226 km above Mars’
surface. However, human error had the craft enter in at a much
closer orbit of 57 km. On September 23, NASA lost
communication with the orbiter., and one month later it was
determined that the orbiter had disintegrated in the atmosphere.
 Chemical Concentrations *
Concentration: An expression of the quantity per unit
volume or unit mass of a substance or how much
solute per given volume (or mass) of solvent.

Solute: minor species

Solvent: major species

Concentrations, as you well know, are normally

expressed in terms of: molarity (M = mol L-1) or molality
(m = mol solute per kg of solvent). Many students have concentration problems of
two types: one pictured above, and one in
handling their units during calculations! Lolz.
Electrolytes are substances that dissolve into ions in
solution, and are classified as strong and weak. The
formal concentration (F) is equivalent to molarity for
only strong electrolytes.
 Other expressions for composition Try these calculations:
Very often, the composition of one pure substance in a
37 wt% HCl, ρ = 1.19 g mL-1
material or mixture is given by the per cent
composition, which is normally expressed in terms of What is the molarity of HCl?
[H+] = 12.1 M
weight or volume.
What is the molality of HCl?
m b = 16.1 m
weight% = solute × 100%
msolvent
V
volume% = solute × 100%
Vsolvent

Be sure you can convert from wt% to molarity!

Another common expression for composition is to use

either parts per million (ppm) or parts per billion (ppb).
1 ppm = 1 μg / 1 mL ≈ 1 μg / 1 g (for H2O)

Atmospheric CO2 now stands at approximately

m m
ppm = substance × 10 6 ppb = substance × 10 9 380 ppm, which means that there are:
Vsample Vsample 380 μg of CO2 per litre of air
Preparing Solutions *
One of the most important pieces of laboratory glassware
for preparing solutions is the volumetric flask. Typically, a
solid (or liquid) reagent or standard is quantitatively
transferred into the flask, followed by dilution to the mark
on its narrow neck.

1. Add reagent, swirl and invert several times.

2. Dilute such that the meniscus rests just above the 500
mL marker

3. Make sure that the flask is very clean, as water

droplets can stick to the upper neck, making the dilution
less accurate
 Dilution *
Once you make a solution in a volumetric flask, you
may be required to produce solutions of lower
concentrations (i.e., diluting the sample).

A simple formula for conducting dilutions is:

M conc × Vconc = M dil × Vdil

In other words, to make up a specific volume of a
diluted solution (Vdil) with a known concentration (Mdil)
from a solution with a known concentration (Mconc), we
would need a precise volume of the initial concentrated
For instance:
The HCl (conc) that is used in the lab is typically
12.1 M. What volume of HCl (conc) would one
need to make a 0.100 M solution by diluting to
1.000 L?

solution (Vconc). (12.1 M) × (x L) = (0.100 M) × (1.000 L)

x = 0.00826 L = 8.26 mL
Note that both sides of this equation give units of
moles!
 Gravimetric Analysis*
Gravimetric analysis is a chemical analysis based upon the accurate weighing
(massing) of a final product. This final product may be the pure substance for which we
are conducting the analysis, or may be another pure substance which contains the
element/compound that we are analyzing for.

Sample analysis: How much iron is there in an iron supplement

tablet? *

1. Tablets containing FeC4H2O4 (iron (ii) fumarate) are ground and

mixed with 150 mL of 0.100 M HCl to dissolve the Fe2+. The solution
is the filtered to remove bits of particulate matter from the tablet.

2. The Fe2+ is oxidized to Fe3+ using an excess (XS) of H2O2.

3. The Fe3+ is reacted with NH4OH to produce a hydrous iron (III)

oxide (FeOOH·xH2O), which is then heated at 900 oC to produce
solid iron oxide (Fe2O3).
 Titrations & Volumetric Analysis

Volumetric analysis is a chemical analysis based on accurate

measurement of a volume of reagent that reacts with the
analyte. Most often, this is accomplished via titration, where the
reagent solution (the titrant) is added to the analyte.

The titrant is usually delivered via a buret, and one monitors the
difference between the initial and final volume markings.

The equivalence point is reached when the amount of titrant

added is exactly equal to the amount of analyte in the receiving
flask. This point is actually a theoretical point - in fact, we never
reach this, but rather hit the end point; the closer the end point
is to the theoretical equivalence point, the better the result!
 Finding the end point
The end point is usually indicated by a change in physical property
of the solution, which may include:

1. a colour change (by eye or spectrophotometric - this may

arise from the substances themselves, or the presence of a
reactive indicator

2. a change in current or voltage (potentiometric)

3. precipitation or dissolution of a substance

In the case above, the first trace of purple colour (i.e., excess
MnO4-) signifies the end point.
 Titration errors and standards
The difference between the end point and equivalence point is known as the titration
error (or titration uncertainty), and is a fact of life! A rough estimate of the titration error
can be obtained by running a blank titration, where the exact same procedure is
conducted without the presence of the analyte (e.g., drip the MnO4- titrant into solution
without the oxalic acid, and see how many drops are needed to actually make the colour
change happen).

All titrations strive for accuracy, and the titrants are almost always made up of very pure
substances (i.e., 99.9% or higher - known as analytical grade reagents). If the pure
reagent is dissolved in a known volume to produce a solution of known concentration,
this is called the primary standard.

In cases where primary standards are not available (e.g., titrations involving
concentrated HCl), the titrant is prepared with an approximately known concentration,
and then used to titrate against a pure analyte or primary standard in order to determine
the precise concentration. This is known as standardization, and this type of titrant is
called a standard solution.
 Direct, back and gravimetric
There are numerous styles of titrations. The
most common is the direct titration, in which
titrant is added to the analyte until the
completion of the reaction.

One may also perform a back titration, which

is useful in instances when its end point is
somewhat clearer than the endpoint for the
direct titration. In this case, a known excess
of reagent is added to the analyte solution,
and a second standard reagent is use to
titrate the excess reagent. One may also use
a back titration in some cases where the end
point is overshot during a direct titration (but
not always!).

Finally, a gravimetric titration involves the delivery of the titrant from a pipette, and the
careful monitoring of titrant concentration as moles of reagent per kg of solution
(molality). The precision with a buret is ca. 0.3%, but with a good analytical balance this
drops to 0.1%
There are numerous styles of titrations. The most common is the direct titration, in which
titrant is added to the analyte until the completion of the reaction.
 Titration calculations*
The concentration of Ca2+ in urine can be determined via the following analysis:

1. Precipitate Ca2+ with oxalate in basic solution.

2. Wash with cold water to remove oxalate, and then dissolve the solid in acid to obtain
Ca2+ and H2C2O4 in solution.

3. Heat the solution to 60 oC and titrate the oxalate with KMnO4 until the purple endpoint
is observed.

There are numerous styles of titrations. The most common is the direct titration, in which
titrant is added to the analyte until the completion of the reaction.
 Summary

The major areas covered in this lecture:

• SI Units - be able to use derived units, and interconvert

• Expressions for concentration - molarity and molality are the most common

• Gravimetric analysis - considerations of stoichiometry and masses of starting

reagents and end products are crucial!

• Volumetric analysis - volume of titrant needed for a stoichiometric reaction of the

analyte is the key point here

• Titrations - the use of primary standards, the meaning of equivalence point and
end point, and direct and back titrations

There are numerous styles of titrations. The most common is the direct titration, in which
titrant is added to the analyte until the completion of the reaction.