Analytical Chemistry
Ch. 1 & 2
Chemical Measurements
Tools of the Trade
Ch. 1
1) units of measurement
2) chemical concentrations
SI units of measurement
See Table 1-1
Table 1-2 lists some quantities that are defined in terms of the fundamental
quantities.
See Table 1-2
Prefixes as Multipliers
Rather than using exponential notation, we often use prefixes from Table 1-3
to express large or small quantities
See Table 1-3
Converting Between Units
Although SI is the internationally accepted system of measurement in science,
other units are encountered.
Useful conversion factors are found in the next slide
See Table 1-4
9e offers the same table, but less organized
Chemical Concentrations
§ A solution is a homogeneous mixture of two or more substances
: solute (minor) + solvent (major)
§ Two types of solutions
1) aqueous solutions: solvent is water
2) non-aqueous solutions: solvent is not water
§ Concentration: how much solute is contained in a given volume or mass
of solution or solvent
: denoted with square brackets
à “[H+]” means “the concentration of H+.”
Chemical Concentrations
Molarity and Molality
Molarity (M): the number of moles of a substance per liter of solution.
Molality (m): moles of substance per kilogram of solvent (not total solution).
moles of solute (mol)
Molarity (M) = (dependent on T )
volumes of solution (L)
Molality (m) = moles of solute (mol) (independent of T )
mass of solvent (kg)
Molality (m): independent of temperature.
Molarity (M): changes with temperature because the volume of a solution
usually increases when it is heated
Percent Composition
§ The percentage of a component in a mixture or solution is usually expressed
as a weight percent (wt%):
Example) A common form of ethanol is 95 wt%;
àmeans 95 g of ethanol per 100 g of total solution.
the remainder is water.
§ Volume percent (vol%) is defined as
Parts per Million and Parts per Billion
ppm, ppb (parts per million, billion)
Sometimes composition is expressed as parts per million (ppm) or parts per
billion (ppb)
à mean grams of substance per million or billion grams of total solution or
mixture.
weight of substance (kg)
ppm = ´ 10 6 (mg/kg) » 1µg/mL = 1mg/L
total weight of sample (kg)
weight of substance (kg)
ppb = ´ 10 9 ( µg/kg) » 1ng/mL = 1µg/L
total weight of sample (kg)
Because the density of a dilute aqueous solution is close to 1.00 g/mL,
à we frequently equate 1 g of water with 1 mL of water, although this
equivalence is only approximate.
For gases,
ppm usually refers to volume rather than mass.
Example) Atmospheric CO2 has a concentration near 380 ppm,
à means 380 μL CO2 per liter of air.
à ex) 미세먼지 in µg / m3
Electrolyte
§ An electrolyte is a substance that dissociates into ions in solution.
§ In general, electrolytes are more dissociated in water than in other solvents.
§ We refer to a compound that is mostly dissociated into ions as a strong
electrolyte.
One that is partially dissociated is called a weak electrolyte.
[Reference]
2-4. Burets
A precisely manufactured glass tube to measure the
volume of liquid delivered through the stopcock at See Fig 2-8
the bottom.
Operating a buret
• wash buret with new solution
• eliminate air bubble before use
• drain liquid slowly
• deliver fraction of a drop near end point
• read bottom of concave meniscus See Fig 2-9
• estimate reading to 1/10 of a division
• avoid parallax error
• account for graduation thickness in readings
14
[Reference]
2-5. Volumetric Flasks
TC: To contain a particular volume of solution at 20OC.
- TC = to contain (volumetric flasks)
- TD = to deliver (pipets and burets)
See Fig 2-11
To reduce adsorption of cations on the glass surface
• washing with acid: replacing cations on the glass surface with H+
• plastic (polypropylene) flask for trace analysis
15
[Reference]
2-6. Pipets and Syringes
delivery of known volumes of liquid
• transfer pipet : the last drop should not be blown out
• measuring (Mohr) pipet : to deliver a variable volume (by difference)
See Fig 2-12
16
[Reference]
Comparison of tolerances of measuring tools
See Table 2-2, 2-3, 2-4
[Reference]
2-6. Pipets and Syringes
How to transfer pipet
• rubber bulb : not your mouth!
• discard one or two pipet volumes of liquid to rinse traces of
previous reagents from the pipet
• touch the tip of the pipet to the side of a beaker -> calibration mark
-> transfer/drain -> holding the tip against the wall of the vessel ->
do not blow out the last drop
• rinse with distilled water : not to dry inside of a pipet
18
[Reference]
2-6. Pipets and Syringes
Micropipets
• delivering volumes of 1 to 1000 µL : disposable PP tip
• do not contaminate the disposable tip :
package/dipenser
• set the volume à depress the plunger à hold pipet See Fig 2-14
vertically, dip it 3-5 mm à slowly release the plunger
to suck up liquid à transfer à touch the tip to the
wall of the receiver à gently depress the plunger à
depress the plunger further to squirt out the last liquid
• The volume of liquid depends on the angle and depth.
Syringe
• discard several volumes of liquid : to wash the glass wall and to
remove air bubble from the barrel
• steel needle is attacked by strong acid
19
[Reference]
2-7. Filtration
See Fig 2-17
20
[Reference]
2-7. Filtration
See Fig 2-18, 19
21
Analytical Chemistry
Ch. 3
Experimental Errors
Chapter 3. Experimental Error
§ There is error associated with every measurement.
§ There is no way to measure the “true value” of anything.
à The best we can do in a chemical analysis is to carefully apply a technique
whose experience tells us is reliable.
§ Repetition of one method of measurement several times tells us the precision
(reproducibility) of the measurement.
§ If the results of measuring the same quantity by different methods agree with
one another,
à then we become confident that the results are accurate
à means they are near the “true” value.
3-1. Significant Figures
§ The number of significant figures
à the minimum number of digits needed to write a given value in scientific
notation without loss of accuracy.
§ For examples:
The number 142.7 has four significant figures
à It can be written as 1.427 × 102.
§ If you write 1.427 0 × 102,
à is not the case for the number 142.7
à The number 1.427 0 × 102 has five significant figures.
à you imply that you know the value of the digit after 7
§ The number 6.302 × 10-6 has four significant figures
à You could write the same number as 0.000 006 302
à The zeros to the left of the 6 are merely holding decimal places.
§ The number 92 500 is ambiguous.
à It could mean any of the following:
§ Zeros are significant when they occur (1) in the middle of a number or (2) at
the end of a number on the right-hand side of a decimal point.
§ The last significant digit (farthest to the right) in a measured quantity always
has some associated uncertainty.
§ The scale of a Spectronic 20 spectrophotometer is drawn in Figure 3-1.
§ The needle in the figure appears to be at an absorbance value of 0.234.
àWe say that this number has three significant figures because the numbers 2
and 3 are completely certain and the number 4 is an estimate.
à The value might be read 0.233 or 0.235 by other people.
See Fig 3-1
3-2. Significant Figures in Arithmetic
§ We now consider how many digits to retain in the answer after you have
performed arithmetic operations with your data.
à Rounding should only be done on the final answer (not intermediate results),
to avoid accumulating round-off errors.
1) Addition & Substraction
§ If the numbers to be added or subtracted have equal numbers of digits,
à the answer goes to the same decimal place as in any of the individual
numbers:
§ The number of significant figures in the answer may exceed or be less than
that in the original data.
§ If the numbers being added do not have the same number of significant
figures,
à we are limited by the least-certain one.
§ The digits 806 4 lie beyond the last significant decimal place.
§ Because this number is more than halfway to the next higher digit,
à we round the 4 up to 5
à that is, we round up to 121.795 instead of down to 121.794
§ If the insignificant figures were less than halfway,
à we would round down.
à For example, 121.794 3 is rounded to 121.794.
§ In the special case where the number is exactly halfway, round to the nearest
even digit.
§ For examples
43.55 à 43.6 if we can only have three significant figures
1.425 × 10-9 à 1.42 × 10-9 if we can only have three significant figures
§ Addition and subtraction:
à Express all numbers with the same exponent and align all numbers with
respect to the decimal point.
à Round off the answer according to the number of decimal places in the
number with the fewest decimal places.
Multiplication and Division
§ In multiplication and division, we are normally limited to the number of digits
contained in the number with the fewest significant figures:
Logarithms and Antilogarithms
§ The base 10 logarithm of n is the number a, whose value is such that n=10a:
§ In Equation 3-1,
à the number n is said to be the antilogarithm of a.
à That is, the antilogarithm of 2 is 100 because 102 = 100
à the antilogarithm of -3 is 0.001 because 10-3 = 0.001
§ A logarithm is composed of a characteristic and a mantissa.
à the characteristic is the integer part
à the mantissa is the decimal part
§ The number 339 can be written as 3.39 × 102
§ The number of digits in the mantissa of log 339 should equal the number of
significant figures in 339.
à The logarithm of 339 is properly expressed as 2.530.
§ The characteristic, 2, corresponds to the exponent in 3.39 × 102
§ In the conversion of a logarithm into its antilogarithm,
à the number of significant figures in the antilogarithm should equal the
number of digits in the mantissa.
à Thus,
§ Here are several examples showing the proper use of significant figures:
