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Analytical Chemistry

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Analytical Chemistry

Amount of substance = mole


Mass = kilogram
Molarity (concentration [c]) = mol L-1
Minor species – solute (analyte) = what we are interested in
Major species – solvent (solution)

𝒂𝒎𝒐𝒖𝒏𝒕 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 (𝒏)


Concentration (c) = 𝒗𝒐𝒍𝒖𝒎𝒆
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏
(𝒗)

𝒎𝒂𝒔𝒔 (𝒎)
Amount (n) =
𝒎𝒐𝒍𝒂𝒓 𝒎𝒂𝒔𝒔 (𝑴)

𝒎𝒂𝒔𝒔(𝒎)
Density (d) =
𝒗𝒐𝒍𝒖𝒎𝒆(𝒗)

Example:
o Syrup contains 10mg codeine in 5mL syrup.
o Tablet contains 10 mg codeine in 5g calcium lactate.
 Codeine molar mass = 299.4 g mol-1
 Syrup density = 1.636g mL-1

1. Express the concentration of codeine in the syrup in mol L-1, g L-1 and mg g-1

- You are given a syrup which has a mix of codeine (solute) and syrup (solution)
- To find the concentration use c = amount of solute/mass of solution
- To find out how much solute (codeine) is inside the syrup convert codeine into appropriate
unit to match the molar mass thus switching mg to g:

Concentration of codeine = amount of solute (n) / mass of solvent (v)

Solve n for solute by: n = m/M


Mass of codeine (m) = 10mg = 0.01 g
Amount of codeine (n) = mass x Molar mass
= 0.01g / 299.4 g mol-1
= 3.34x10-5mol

- Now find out the amount of solvent (syrup)

Concentration of codeine = 3.34x10-5mol / mass of solvent

Solve mass (v) for solvent by: density = m / v


Mass of syrup (m) = density x volume of codeine
Need to use mL here to get rid of
Mass of syrup (m) = 1.636 g mL-1 x 5 mL
the density mL unit
= 8.180 g

Volume of solvent (v) for syrup = 5mL = 0.005 L


Need volume in L to solve everything
in L-1 to answer question
- Thus to answer the question for the concentration of codeine in the syrup:
 C = n/v
 For mol L-1 = 3.34x10-5 mol / 0.005L = 6.68x10-3mol L-1
 For g L-1 = 0.01g / 0.005 L = 2 g L-1
 For mg g-1 = 10 mg / 8.18g = 1.22 mg g-1

2. Express the concentration of codeine in the tablet in mol kg-1, g g-1 and mg g-1

- To find the concentration of the tablet use c = amount of codeine / mass of solvent
- We already found concentration and amount, but we have a new mass of solvent

Mass of solvent tablet = 5g = 0.005kg Need mass in kg to solve the


question for mol kg-1

- Thus to answer the question for the concentration of codeine in the tablet:
 C = n/v
 For mol kg-1 = 3.34x10-5 mol / 0.005kg
 For g g-1 = 0.01 g / 5g = 2x10-3g g-1
 For mg g-1 = 10 mg / 5g = 2mg g-1

Problem 2: Seawater contains 2.7g of NaCl per 100mL.


NaCl molecular weight = 58.5g mol-1
Density of seawater = 1.38g mL-1

1. Express the concentration of NaCl in seawater in mol L-1, g L-1 and mg g-1

- Concentration of NaCl = amount of solvent (n) / mass of solution (v)

Concentration of NaCl = n / v

Solve n for solvent by: n = m / M


n = 2.7g / 58.5 g mol-1
= 0.046 mol

Concentration of NaCl = 0.046 mol / v

Solve v for solution by: density = m / v


Mass of solution (v) = density x mass
Mass (v) = 1.38g mL-1 x 100mL
= 138g

Volume = 100mL = 0.1 L

 For mol L-1 = 0.046 mol / 0.1 L = 0.46mol L-1


 For g L-1 = 2.7g / 0.1 L = 27g L-1
 For mg g-1 = 2700mg (converted from 2.7g) / 138g = 19.57mg g-1
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 (𝒎𝒐𝒍)
Molality (m) = = ___ mol kg-1
𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 (𝒌𝒈)

Molality is independent of temperature.

Example:
An aqueous solution of antifreeze contains 6.067mol L-1 ethylene glycol (Mr = 62.07g mol-1) and has
a density of 1.046g mL-1.

1. Find the mass of 1.0L of this solution and the mass of ethylene glycol.

- Need to work out mass for solute.

Solve m by: Amount of ethylene glycol (n) = mass of solute (m) / Molar mass (M)
n=m/M
Therefore m = n x M
n = 6.067 mol L-1 (x 1L) = 6.067 mol
Mass (m) = n x M
Mass (m) = 6.067mol-1 x 62.07g mol-1
= 376.6g

- Need to work out mass for solvent (in this case total aqueous solution).

Solve m by: Mass for solvent (m) = density (d) x volume (v)
m=dxv
m = 1.046g mL-1 x 1000 mL Converted from 1L in question
m = 1046g

2. Find the molality of ethylene glycol in this solution.

- Subtract the mass of solute from mass of total solution to get mass of only aqueous product:

1046g – 376.6g = 669.4g = 0.669kg

- Put into molality equation:

Molality (m) = moles of solute (mol) / moles of solvent aqueous solution (kg)
Molality (m) = 6.067 mol / 0.669kg
= 9.06mol kg-1
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
Volume percent (vol%) = 𝒙 𝟏𝟎𝟎
𝒗𝒐𝒍𝒖𝒎𝒆 𝒐𝒇 𝒕𝒐𝒕𝒂𝒍 𝒔𝒐𝒍𝒖𝒕𝒊𝒐𝒏

Example:
Find the molarity of 37 wt% of HCl. The density of HCl solution is 1.19g mL-1. Molar mass of
HCl is 36.46g mol-1.

- To find the molarity of HCl we use the equation:

Molarity (n) = mass of HCl (m) / Molar mass of HCL (M)

To solve for mass of HCl (n) in the total solution: density = mass / volume of total
Volume = density x mass
= 1.19g mL-1 x mass

Assume for 1L of total solution so that means 1000mL of total solution mass.

Thus… Volume of total solution = 1.19g mL-1 x 1000mL


= 1190g

- Therefore to solve m; we find 37% of the total volume solution to get ONLY the mass of HCl.

37% x 1190g = 440.3g

- To solve for molarity (n) = m / M


= 440.3g / 36.46g mol-1
= 12.07mol-1

- Because the molarity unit is mol L-1; you must convert thus:
12.07mol-1 x 1L = 12.07mol L-1

Parts per million (ppm) and parts per billion (ppb)

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒖𝒃𝒔𝒕𝒂𝒏𝒄𝒆
𝒑𝒑𝒎 = 𝒙 𝟏𝟎𝟔
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒂𝒎𝒑𝒍𝒆

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒖𝒃𝒔𝒕𝒂𝒏𝒄𝒆
𝒑𝒑𝒃 = 𝒙 𝟏𝟎𝟗
𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒂𝒎𝒑𝒍𝒆

*No units are used because they will be cancelled out.

- Because the density of dilute aqueous solution is 1.00 g mL-1, 1g of water is 1 mL of water

1 ppm = 1 µg mL-1 = 1 mg L-1


1 ppb = 1 ng mL-1 = 1 µl-1
Example:

Soil contains 2 mg of lead. Each kg of soil has concentration 2ppm (w/w). Thus:

Mass of solute (lead) = 2 mg = 2 x 10-3 g


Mass of sample (soil) = 1 kg = 1 x 10-3 g

- Use equation:

mass of substance
ppm = x 106
mass of sample

2𝑥10−6
= 𝑥 106 = 2ppm (w/w)
1𝑥103

Types of errors

Systematic error – determinate errors (errors we know e.g. burrette)


Constant in magnitude (bias)
Removable by suitable calibration or correction

Random error – indeterminate errors (experimental errors e.g. meniscus reading)


Vary in magnitude and direction
Can be minimized but not removed

Blunders – e.g. misread scale

Precision – reproducibility of a result

Accuracy – how close the measured value is to the true value

Uncertainties

Absolute uncertainty (margin of uncertainty associated with a measurement)

𝒆 = √𝒂𝟐 + 𝒃𝟐 + 𝒄𝟐 … (for addition and subtraction)


Example: Burette: 50.00 ± 0.02mL
Titration: 16.88 ± 0.02mL

Total = (50.00-16.88) ± ?

Absolute uncertainty (?) =


𝑒 = √𝑎2 + 𝑏 2 + 𝑐 2 …

𝑒 = √0.022 + 0.022 = 0.028mL


E = 15.14 ± 0.03 mL
Relative uncertainty (relative uncertainty expressed as percentage)
𝒂𝒃𝒔𝒐𝒍𝒖𝒕𝒆 𝒖𝒏𝒄𝒆𝒓𝒕𝒂𝒊𝒏𝒕𝒚
% Relative uncertainty = 𝒙 𝟏𝟎𝟎
𝒎𝒆𝒂𝒔𝒖𝒓𝒆𝒎𝒆𝒏𝒕 𝒗𝒂𝒍𝒖𝒆

% 𝒆 = √𝒂%𝟐 + 𝒃%𝟐 + 𝒄%𝟐 (for multiplication and division using relative


uncertainty)

Example: for previous question:

0.03
% relative uncertainty = 𝑥 100 = 0.1981 %
15.14

Example question for combining addition and subtraction


An analyst weighs 5.0435 ± 0.0001g of paracetemol into a weighing bottle, empties the
contents of the bottle into a 25.0 ± 0.01 mL volumetric flask and measures the weight of the
empty weighing bottle as 0.0004 ± 0.0001 g. The flask is made up to the mark with methanol.
Calculate the concentration of the solution in g mL-1.

Concentration = 5.0435 ± 0.0001g

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