Measurement and Data

Processing
Ms.Peace
 Lesson 1

11.1 Uncertainties and Errors in Measurements and Results

Qualitative vs. Quantitative
▶ Qualitative data includes all non-numerical
information obtained from observations not from
measurement. (Chemical and Physical Properties)
▶ Solubility
▶ Melting Point

▶ Quantitative data are obtained from measurements,

and are always associated with random
errors/uncertainties, determined by the apparatus, and
by human limitations such as reaction times
▶ Amount
▶ Concentration
Qualitative vs. Quantitative
What Is An Uncertainty?
▶ No measuring instrument (be it a plastic ruler or the world’s
most accurate thermometer) is perfectly accurate

▶ When you make any measurement, there always is some

uncertainty as to the exact value.

▶ For example:
▶ The ruler says this red line is 3.5 cm long
▶ Due to imperfections in the design and manufacturing of the ruler,
I can’t be sure that it is exactly 3.500 cm, just something close to
that, perhaps 3.492. or 3.521
Uncertainty in Measurements
▶ Data involving exact numbers-the values are known
exactly and there is no uncertainty
▶ A dozen donuts
▶ 8 students

▶ Data involving inexact numbers-there is a degree of

uncertainty
▶ Height of a student
▶ Temperature of a student
Measuring Uncertainties

▶ Most equipment manufacturers know

the level of uncertainty in their
instruments, and will tell you.

▶ For example:
▶ The instruction manual that came with my
ruler tells me it is accurate to +/- 0.05 cm.
▶ This means my 3.5 cm line is actually
anywhere between 3.45 and 3.55 cm long
▶ Importantly: we have no way of knowing
where in this range the actual length is,
unless we use a more accurate ruler
How Big Are The Uncertainties?
▶ Most good apparatus will have the
uncertainty written on it, so make a
note of it.

▶ Where this is not the case, use half

the smallest division:
▶ For example: if a balance can measure
to two decimal places, the uncertainty
would by +/- 0.005 g

▶ When manually measuring time, you

should round to the nearest whole
second, and decide the uncertainty
based on the nature of your
measurement.
Analogue Instruments

Beaker Graduated Volumetric

Cylinder Flask

10 mL $4.44 $13.77 $29.53

250 mL $3.86 $33.21 $60.55

Balances
Top Pan Balance: measure
mass
in a school lab setting

Analytical Balance: measure mass

to a high degree of precision.
Shutters allow the reduction
of air flow and dust collection
Balance Precision

Balance reads to 1 place = $118.95

Balance reads to 0.1 place = $159.95
Balance reads to 0.01 place = $277.90
Balance reads to 0.001 place = $407.40
 Precision vs Accuracy
▶ Closeness of agreement ▶ Closeness of the agreement
between independent test between the result of a
results obtained by applying measurement and the true
the experimental procedure value of the measurand-the
under stipulated conditions
particular quantity to be
measured
▶ The smaller the random part of
the experimental errors, the
more precise the procedure
Significant Figures
▶ The number of digits reflecting the precision of a given
measurement
▶ The greater the certainty the greater the certainty
about the numerical value of the measured or
calculated quantity
Scientific Notation

Measurement Scientific Notation # of Sig Figs

135.680g 1.35680 x 102g 6

0.00620dm3 6.20 x 10-3dm3 3

300kg 3 x 102kg 1
Scientific Notation
▶ Multiplying or Dividing
▶ The result should be expressed based on the
measurement with the smallest number of significant
figures

▶ Adding or Subtracting
▶ The result should be expressed based on the
measurement with the smallest number of decimal places
Experimental Errors
Systematic Errors
▶ Associated with flaw in the actual experimental design
or with the instrumentation used

▶ Imply that the measured quantity will always be

greater or less than the true value

▶ Types of systematic errors:

▶ Instrumentation errors
▶ Experimental methodology
▶ Personal errors
Experimental Errors
Systematic Errors
▶ Faulty gas syringes that have associated leakage
▶ Instrumentation Error
▶ Poorly insulated calorimeter in a thermochemistry
experiment
▶ Experimental Methodology Error
▶ The exact color of a solution at its end point
▶ Personal Error
▶ Systematic error can be reduced by adopting greater
care to the experimental design
▶ Such errors are consistent and can be detected and
ultimately corrected
▶ Systematic errors will affect accuracy of results
Systematic Error
Experimental Errors
Random Errors
▶ Occur because of uncontrolled variables in an
experiment and therefore cannot be eliminated
▶ Can be reduced by repeating measurements
▶ Affect the precision of the results
▶ Examples
▶ Estimating quantity which lies between marked
graduations of a particular instrument (burette, graduated
cylinder)
▶ Not being able to read an instrument due to fluctuations
in readings (temperature, airflow)
▶ Reaction time
 Absolute and Relative Uncertainty
▶ Absolute uncertainty is the actual ▶ This is the size of the uncertainty relative
size of the uncertainty in the units to the value measured, and is usually
used to measure it. expressed as a percentage

▶ This is what the previous slide ▶ Relative uncertainty can be calculated by

referred to dividing the absolute uncertainty by the
measured value and multiplying by 100

▶ In our ruler example, the absolute ▶ In our ruler example, the relative
uncertainty is uncertainty is
+/- 0.05 cm ▶ 0.05 / 3.5 x 100 = 1.4%

▶ To minimise absolute uncertainty, ▶ To minimise relative uncertainty, you

you should use the most accurate should aim to make bigger
equipment possible. measurements
How do uncertainties affect my calculations?
▶ If the numbers you are putting into a calculation are
uncertain, the result of the calculation will be too

▶ You need to be able to calculate the degree of uncertainty

▶ The Golden Rules:

▶ When adding/subtracting: add the absolute uncertainty

▶ When multiplying/dividing: add the relative uncertainty

Absolute and Relative Uncertainty
▶ Absolute uncertainty: margin of uncertainty associated
with the result from a given measurement, ΔA
▶ Relative uncertainty: ratio comparing the size of the
absolute uncertainty, ΔA, to the size of the measured
experimental result
relative uncertainty = ΔA
A
▶ Experimental results should be reported as:
experimental result = (A ± ΔA) unit
 Example: A Titration
▶ A calibrated burette has an absolute uncertainty of ±0.02
cm3. During a titration, the volume of a 0.15mol dm-3
solution of hydrochloric acid at the end point was recorded
as 12.25cm3. Calculate the associated relative uncertainty

▶ Absolute uncertainty = ±0.02 cm3

▶ Measured experimental result (A) = (12.25 ±0.02) cm3
▶ Relative uncertainty = ΔA = 0.02cm3
A 12.25cm3 = 2 x 10-3
▶ Relative uncertainty percentage = 0.2%
Example 2: A rate of reaction
▶ In an experiment on the rate of a reaction, a student timed how long it
would take to produce 100 cm3 of gas, at a variety of different
temperatures. At 30OC, it took 26.67 seconds. The gas syringe used was
accurate to +/- 0.25 cm3. What is the average rate of reaction, and what
is the relative uncertainty in this value?

▶ Rate = volume / time = 100 / 27 = 3.70 cm3s-1

▶ Time is rounded to the nearest whole second as human reaction times do not
allow for 2 decimal places of accuracy
▶ Absolute uncertainty of volume: +/- 0.25 cm3
▶ Absolute uncertainty of time: +/- 0.5s
▶ This is an approximation, taking into account reaction time and the difficulty of
pressing stop exactly at 100 cm3.
▶ You should make similar approximations whenever you are manually recording
time, and should write a short sentence to justify them
Example 2 continued
▶ Relative uncertainty of volume
▶ % Uncertainty = (absolute uncertainty / measured value) x 100
= 0.25/100 x 100 = 0.25%

▶ Relative uncertainty of time

▶ % Uncertainty = (0.5 / 27) x 100 = 1.85%

▶ Relative uncertainty of rate

▶ % Uncertainty (rate) = % uncertainty (volume) + % uncertainty
(time) = 0.25 + 1.85 =
2.10%
▶ The relative uncertainties were added as the rate calculation
required a division calculation
Propagation of Uncertainty
▶ After identifying the uncertainties associated with
experimentally measured quantities, the next step is to
figure out how these different uncertainties combine to
give the resultant uncertainty
▶ Rule 1:
▶ When adding or subtracting measurements, the absolute
uncertainty associated with the net measured parameter is the
square root of the sum of the squares of the absolute uncertainty

▶ Rule 2:
▶ When multiplying or dividing measurements, the relative
uncertainty associated with the net measured parameter is the
square root of the sum of the squares of their relative uncertainties
Percent Error

▶ The literature value for the standard enthalpy change

of the decomposition reaction of calcium carbonate
was found to be +178.1kJ. The experimental value was
found to be +172.0kJ
% error = 178.1-172.0 x 100%
178.1
= 3.4%
 Lesson 2

11.2 Graphical Techniques

Graphical Techniques
▶ Graphical techniques are effective means of
communicating the effect of an independent variable
on a dependent variable, and can lead to the
determination of physical quantities
▶ Sketched graphs have labelled but unscaled axes, and
are used to show qualitative trends, such as variables
that are proportional or inversely proportional. Units
generally would not be shown on a sketch, only the
variables
▶ Drawn graphs have labelled and scaled axes, and are
based on quantitative measurements. Drawn graphs
always diplay the appropriate units for variables
Key Terms
▶ Dependence: any statistical relationship between two
sets of data or between two random variables
▶ Independent Variable: the “cause” is plotted on the
x-axis
▶ Dependent Variable: the “effect” is plotted on the
y-axis
▶ Correlation: statistical measure and technique that
indicates the degree and relationship between two
sets of variables
Key Terms
▶ Positive Correlation: where the two variables increase
or decrease in parallel to one another
▶ Negative Correlation: one variable increases while the
second decreases or vice versa
▶ Correlation Coefficient: measure of the strength of the
relationship between two variables, r
▶ r= +1 : perfect positive linear relationship
▶ r= 0: no linear relationship exists
▶ r= -1: perfect negative linear relationship
▶ Scatter Plots: show the scatter of various points on a
graph
Slope or Gradient of Line, m
▶ The tangent of the angle that the line makes with the
positive direction of the x-axis.

▶ Incline: + slope

▶ Decline: - slope
The Intercept, c
▶ The point where the line cuts the y-axis at x=0
▶ The intercept can be found by:
▶ Extrapolation: extending the line
▶ Equation of the line as long as the slope is known y=mx + c
Best-Fit Line
▶ Data obtained from an experiment does not always
contain data points that lie exactly along the line
▶ Best fit line does not always necessarily contain all the
experimental data points
 Lesson 3

11.3 Spectroscopic Identification of Organic Compounds

Degree of Unsaturation
▶ The degree of unsaturation or index of hydrogen
deficiency (IHD) can be used to determine from a
molecular formula the number of rings or multiple
bonds in a molecule

▶ Double bond-1 degree of unsaturation

▶ Triple bond-2 degrees of unsaturation
▶ RIng: 1 degree of unsaturation
▶ Aromatic ring-4 degrees of unsaturation
Degree of Unsaturation
Benzene
-One ring
- Three double bonds
IHD: 4

Cyclopentadiene
Cyclobutane
-One ring -One ring
IHD: 1 -Two double bonds
IHD: 3
Degree of Unsaturation
2-acetylbenzoic acid (aspirin)
-One ring
-Five double bonds
IHD: 6

Ethyne
-One triple bond
IHD: 2
Degree of Unsaturation
CcHhNnOoXx X is a halogen (F, Cl, Br, or I)

IHD= 0.5(2c+2-h-x+n)

▶ Given C4H8O2 deduce the IHD

c=4 h=8 n=0 o=2 x=0
IHD=0.5(8+2-8-0-0) = 1
The molecule must contain either one double bond or
one ring. There are several isomers of C4H8O2
Degree of Unsaturation
Possible isomers of C4H8O2 with IHD of 1
Electromagnetic Spectrum

Energy, E is directly related to the frequency, , and

inversely related to wavelength, λ
E=h =hc c (speed of light): 3.00 x 108 ms-1
λ h (Plank’s constant): 6.626 x 10-34 J s
Electromagnetic Spectrum
▶ The various regions are the basis of different types of
spectroscopy (the study of the way matter interacts
with radiation) and various techniques are used to
identify the structures of substances
Regions of the EMS
▶ X-rays: high energy, cause electrons to be removed from the
inner energy levels of atoms. Diffraction patterns can lead to
information such as bond distances and bond angles in a
structure
▶ Basis for x-ray crystallography
▶ Visible light and Ultraviolet (UV) light: give rise to electronic
transitions and hence this type of spectroscopy gives
information about the electronic energy levels in an atom or
molecule.
▶ Basis for UV-vis spectroscopy
▶ Infrared Radiation: causes certain bonds in a molecule to vibrate
(stretch and bend) and provides information on the functional
groups present.
▶ Basis of IR spectroscopy
Regions of the EMS
▶ Microwaves: cause molecular rotations and can give
information on bond lengths
▶ Radio Waves: cause nuclear transitions in a strong
magnetic field because radio waves can be absorbed
by certain nuclei, which causes their spin states to
change.
▶ Nuclear Magnetic Resonance (NMR) is based on this and
information on different chemical environments of atoms
can be deduced, which leads to information on the
connectivity of the atoms present in a molecule
Types of Spectroscopy
▶ Three different types of spectroscopy that form the
cornerstone of the spectroscopic identification of
organic molecules
▶ Infrared (IR) spectroscopy: determines the bonds in
organic molecules
▶ Proton nuclear magnetic resonance (1H NMR)
spectroscopy: shows the chemical environments of
isotopes (mostly used with hydrogen)
▶ Mass spectrometry (MS): determines the relative atomic
and molecular masses. Fragmentation patterns are useful
with organic
Infrared Spectroscopy
▶ IR radiation does not have sufficient energy to result in
electronic transitions but can cause molecular
vibrations which result from the vibration of certain
groups of molecules about their bonds
▶ Helps identify various functional groups in a molecule
▶ Vibrational transitions correspond to definite energy
levels
Infrared Spectroscopy
▶ Spring model: covalent bonds are thought of as
springs that have vibrations
▶ Spring can be stretched (symmetrically and
asymmetrically), bent, or twisted
▶ The force required to cause the vibration is based on
Hooke’s law
Infrared Spectroscopy
▶ Lighter atoms will vibrate at higher frequencies and heavier
atoms will vibrate at lower frequencies
Molecule Bond Enthalpy/ kJ mol-1 Wavenumber/cm-1

H-Cl 431 2886

H-Br 366 2559

H-I 298 2230

▶ The same applies for multiple bonds

▶ Imagine two atoms connected by a spring, the stronger the
bond connecting the two atoms the tighter the string will be and
therefore more energy is required to stretch it
▶ For diatomic molecules only one form of vibration is possible,
stretching
Infrared Spectroscopy
▶ Polyatomic species may have several modes of
vibration
▶ Symmetric stretch
▶ Asymmetric stretch
▶ Symmetric bend
Infrared Spectroscopy
▶ For a covalent bond to absorb IR radiation there must
be a change in the molecular dipole moment
associated with the vibration mode
non-polar
IR inactive

non-polar
IR inactive asymmetric stretch
symmetric bend
Infrared Spectroscopy
▶ The absorbance, A, is related to the transmittance by
A=-log10T
▶ IR spectrum is a plot of the percentage transmittance,
%T versus the wavenumber in cm-1, where %T ranges
from 0% to 100%.
▶ Functional groups can be identified
▶ YOU WILL NEED TO BE VERY FAMILIAR WITH THE
NAME AND STRUCTURE OF FUNCTIONAL GROUPS
Infrared Spectroscopy
▶ A bond will only interact with IR radiation if it is a polar
covalent bond

▶ Non-polar bonds DO NOT absorb IR radiation

▶ Intensity depends on dipole moment of bonds:

▶ Strong polar bonds produce strong bands
▶ Bonds with medium polarity produce medium bonds
▶ Weak bonds produce weak bands
Infrared Spectroscopy
Functional Groups
Infrared Spectroscopy
▶ Typical proton shift
Infrared Spectroscopy
Infrared Spectroscopy
1
H NMR Spectroscopy
▶ Gives information on the different chemical
environments of hydrogen atoms in a molecule
▶ Considered the most important structural technique
available to organic chemists
1
H NMR Spectroscopy
▶ Nuceli of hydrogen atoms can exist in two possible
spin states and behave as tiny magnets
▶ When nuclei are placed in magnetic fields the spin
states may align with the magnetic field or against it
creating two nuclear energy levels
1
H NMR Spectroscopy
▶ The position of the NMR signal relative to a standard
(tetramethylsilane, TMS) is the chemical shift, ,
expressed in parts per million (ppm) of the proton
▶ for TMS is 0 ppm
1
▶ H NMR spectrum shows the number of different
chemical environments in which the hydrogen atoms
are found
1
H NMR Spectroscopy
Typical proton shift
1
H NMR Spectroscopy
1
H NMR Spectroscopy
1
H NMR Spectroscopy
▶ Integration trace: shows the relative number of
hydrogen atoms present

▶ Magnetic Resonance Imaging (MRI): gives a 3D view of

organs in the human body
1
H NMR Spectroscopy
Number of peaks

1 chemical environment 2 chemical environments

1 peak 2 peaks

3 chemical environments
3 peaks
Mass Spectrometry (MS)
▶ When a gaseous molecule is ionized its molecular ion,
M+ is formed
▶ The molecular ion peak in a mass spectrum
corresponds to the molecular mass of the compound
▶ Due to the highly energetic ionization process
involved in a mass spectrometer, the molecule can
break up into fragments, some being ions
▶ The fragmentation pattern provides further
information on certain functional groups present in a
molecule
Mass Spectrometry (MS)

Ar= (31.5)(23) + (32.5)(10) + (63)(46) + (65)(21) / 100

Ar= 53.2
Mass Spectrometry (MS)

Heavier
Lighter particles
particles
Mass Spectrometry (MS)
▶ When the vaporized organic sample passes into the
ionization chamber, it is bombarded by a stream of
electrons
M(g) + e- →M+(g) + 2e-

▶ The M+ ion is known as the molecular ion

▶ Fragments are produced to produce information about

structure
Mass Spectrometry (MS)
▶ Examples:
▶ (Table 15 from Data Booklet)
▶ (Mr-15)+ results from the loss of -CH3
▶ (Mr-17)+ results from the loss of -OH
▶ (Mr-29)+ results from the loss of -CHO or -CH2CH3
▶ (Mr-31)+ results from the loss of -OCH3
▶ (Mr-45)+ results from the loss of -COOH
Mass Spectrometry (MS)

Mr
C2H3O+
COOH+
CH3+

Peak at m/z 45 Peak at m/z 43 Peak at m/z 15

(60-45)=15 mass loss (60-43)=17 mass loss (60-15)=45 mass loss
-CH3 -OH -COOH
 Lesson 4

21.1 Spectroscopic Identification of Organic Compounds

High Resolution 1H NMR
High Resolution 1H NMR
▶ Shows further splitting of some absorptions
▶ Splitting patterns result from spin-spin coupling
Higher energy
Less stable

Lower energy
More stable
+1/2 -1/2
High Resolution 1H NMR
▶ Four combination possible:
▶ Ha1 and Ha2 magnetic moment aligned with B0 (deshields
Hb, so signal is shifted downfield to higher )
▶ Ha1 magnetic moment aligned with B0 and Ha2 magnetic
moment aligned against B0
▶ Ha1 magnetic moment aligned against B0 and Ha2
magnetic moment aligned with B0
▶ Ha1 and Ha2 magnetic moments aligned against B0 (shields
Hb, so signal is shifted upfield to a lower )

B0
High Resolution 1H NMR

Increased magnetic field strength

High Resolution 1H NMR

▶ Pascal’s triangle can be used to deduce the splitting

patterns
▶ This gives the ratio of intensities
High Resolution 1H NMR
▶ Spin-Spin coupling depends on the way hydrogens
are related to each other in the bonding arrangements
within the molecule
▶ Two Rules
1. If a proton Ha, has n protons as its nearest
neighbors, that is n x Hb, then the peak of Ha will
split into (n+1) peaks
2. The ratio of the intensities of the lines of the split
peak can be deduced from Pascal’s triangle
High Resolution 1H NMR

1 : 1

1 : 2 : 1

1 : 3 : 3 : 1
High Resolution 1H NMR
High Resolution 1H NMR

Heights can be used to obtain the ratio of the number of

protons in each environment
High Resolution 1H NMR
▶ TMS is used because the 12 protons are in the same
chemical environment causing a single peak which will
be strong
▶ = 0 ppm, protons in organic compounds will
typically absorb more downfield in relation to TMS
▶ TMS is inert so it is fairly unreactive and will not
interfere with the sample
being analyzed
▶ It can be easily removed from
the sample because it is volatile
with low boiling point
High Resolution 1H NMR
▶ Protons in water molecules within human cells can be
detected by magnetic resonance imaging (MRI), giving
3D view of organs in the human body
▶ MRI instruments can detect chemical changes in the
brain
▶ This has allowed scientists to pinpoint specific regions
of the brain itself where brain
activity is taking place and gain
an understanding of chemical
principles of the thought process
X-Ray Crystallography
▶ The structural technique of single crystal X-ray
crystallography can be used to identify the bond
lengths and bond angles of crystalline structures, both
organic and inorganic
X-Ray Crystallography
▶ The X-rays strike the crystals and are diffracted into
many specific directions depending on the location of
electrons within the sample
▶ The 3D model of the electron density can be created
and the mean position of the atoms are calculated