You are on page 1of 34

Thushan Hettige VCE Unit 3 Chemistry

         

AREA OF STUDY 1: CHEMICAL ANALYSIS Principles: It’s about WHAT the stuff is, and HOW MUCH there is! STUDY DESIGN:
• volumetric analysis including determination of excess and limiting reagents and titration curves: simple and back titrations, acid-base and redox titrations • gravimetric analysis • calculations including amount of solids, liquids and gases; concentration; volume, pressure and temperature of gases • the writing of balanced chemical equations, including the use of oxidation numbers to write redox equations, and the application of chemical equations to volumetric and gravimetric analyses • principles and applications of chromatographic techniques (excluding features of instrumentation and operation), and interpretation of qualitative and quantitative data from: – thin layer chromatography (TLC), including calculation of Rf – high performance liquid chromatography (HPLC) and gas chromatography (GC) including Rt and the use of a calibration graph to determine amount of analyte • principles and applications of spectroscopic techniques (excluding features of instrumentation and operation), and interpretation of qualitative and quantitative data from: – atomic absorption spectroscopy (AAS) including electron transitions and use of calibration graph to determine amount of analyte – infrared spectroscopy (IR) including use of characteristic absorption bands to identify bonds – proton and carbon-13 nuclear magnetic resonance spectroscopy (NMR) including spin, the application of carbon-13 to determine number of equivalent carbon environments; and application of proton NMR to determine structure: chemical shift, areas under peak and peak splitting patterns (excluding coupling constants), and application of n+1 rule to simple compounds – visible and ultraviolet spectroscopy (visible-UV) including electron transitions and use of calibration graph to determine amount of analyte – mass spectroscopy including determination of molecular ion peak and relative molecular mass, and identification of simple fragments • matching analytical technique/s to a particular task: single and combined techniques.

A summarised version of AOS 1: Wet-way analysis 1. Stoichiometry and Calculations 2. Gravimetric Analysis 3. Volumetric Analysis Instrumental Analysis 4. Chromatography 5. Spectroscopy *IR and NMR analysis will be in the AOS 2 notes, because they coincide with organic very well. In study design they are found in AOS 1. HIGHLY RECOMMEND this website: www.chemguide.co.uk

   

 

1  

Thushan Hettige VCE Unit 3 Chemistry
         

Before we embark on our chemical analysis work, we need to be able to perform stoichiometric calculations. Hence, we will address this section first. 1. STOICHIOMETRY AND CALCULATIONS

Formulas// Below is the list of formulas that you may be familiar with: n = m/M mol = g/(g mol-1) n = cV mol = mol L-1 x L pV = nRT OR

You could memorise the formulas, or you could think about these conceptually, or you could play with units (as per the second line). However, because R = 8.31 and is a universal gas constant, p, V, n and T have to be in specific units: P is in kPa V is in L T is in Kelvins (NOT DEGREES) Excess reagent notes//

Accuracy – “Sig Figs”//
      2  

Thushan Hettige VCE Unit 3 Chemistry
         

Here are the rules for quoting results in a nutshell: Adding/Subtracting: the result is only as accurate as the data with the least number of decimal places eg. 2.463 (3 dp) + 1.2 (1 dp) = 3.7 (1 dp) Least accurate value is to 1 dp.

Worked Example 1.1:

It is known that 0.2402 mol of NaOH was added to a reaction flask containing NH4+ ions, and that 0.2104 mol is remaining in the flask after reaction with the ammonium ions. What is the amount of NaOH, in mol, that has reacted with the ammonium ions? (Express your answer to the correct accuracy)

Worked solution:

   

 

3  

294 g sample of Na2CO3 was dissolved into a 500. Worked Example 1.2: 200 mL of a 0.66 (3 sf) Least accurate value is to 3 sf.00 mL aliquot extracted and added into a conical flask. in mol. What is the amount. 1. and a 20.265 (4 sf) x 1. What is the amount.31 (3 sf) = 1. of HCl in the beaker? Worked solution: Worked Example 1.3: A 1.1322 M HCl solution was added into a beaker.Thushan Hettige VCE Unit 3 Chemistry           Multiplying/Dividing: the result is only as accurate as the data with the least number of significant figures eg. Worked solution:       4   . of Na2CO3 present in the conical flask? Express your answer to the correct number of significant figures.0 mL volumetric flask. in mol.

Worked solution: Worked Example 1.4: Calculate [H+] for a solution of pH 1. 10-4. Worked solution:       5   .0342 M.4: Calculate the pH of a solution that has a [H+] of 0.759 (3 sf à 3 dp) Worked Example 1. b is to p significant figures eg. d is to p decimal places eg.Thushan Hettige VCE Unit 3 Chemistry           Exponentials: 10a = b If a is to p decimal places.76 = 1. log10 (1.74 x 10-4) = -3.7 x 10-5 (2 dp à 2 sf) Logarithms: log10 c = d If c is to p significant figures.34.

which is quite odd.01g/mL = 1 g/(100 mL) 1 ppm = 1 µ g/mL = 1 mg/L 1 ppb = 1 ng/mL = 1 µ g/L I’m being a little detailed here so that on the chance that you forget these equivalent measurements you could quickly derive them. ppm and ppb. Worked Example 1.050/1 x 100% = 5.00 mL solution with the iron tablet dissolved is 139 ppm.050 g of NaCl dissolved in 1 mL of water. and (especially for dilute solutions) the mass of solute is considered negligible. The % is a part per 100. So if we have 0. ppm a part per million and ppb a part per billion.0% (w/v) solution of NaCl.5: UV-visible spectroscopy was used to measure the concentration of iron in an iron sulphate tablet. we can say that we have a 0. Those three measurements are measuring a ratio between a mass and a volume. It is found that the concentration of iron in a 20. What is the amount.Thushan Hettige VCE Unit 3 Chemistry           Units The unit conversions are as follows: x 10-9 nano n x 10-6 micro µ x 10-3 milli m x 10-0 x 103 kilo k x 106 mega M The more ‘iffy’ unit conversions are the % (w/v). The basis of these calculations is the assumption that: 1 g = 1 mL ßà 1000 g = 1 L as the density of water is about 1 g/mL. The three measurements are analogous to each other. of iron present in the tablet? Worked solution:       6   . This spawns the following equivalent measurements: 1% (w/v) = 0. in mol.

Thushan Hettige VCE Unit 3 Chemistry           CHEMICAL ANALYSIS Now that we have the skills to perform calculations. Silver chloride is white. hearing (NOT touch. In other cases. Imagine trying to find a needle in a haystack or trying to tell the difference between sulphuric and hydrochloric acids and water – which are all clear. We can exploit this and that yields our quantitative analysis. To work out WHAT the stuff is. For instance. we need to know the central concept involved in all of these techniques. taste or smell. with no consideration as to its amount. we need to use our senses – sight. Hence. it is now time to cover the analytical techniques. To work out HOW MUCH there is. The problem is that we cannot see individual atoms. we need to work out a property of the chemical that increases or decreases proportionally according to the amount of chemical there is. What we need to do is find a DIFFERENCE between all of these chemicals that we can test for and exploit. Therefore we can tell which chemical is which. Quantitative: where one wants to determine the amount/concentration of a certain compound – so how much compound there is. The central concept is this: chemical analysis is about WHAT the stuff is.       7   . we can do this by just looking at the solids. this is impossible. for obvious reasons). That is the basis of qualitative chemical analysis. here are the definitions of qualitative and quantitative analysis: Qualitative: where one simply wants to determine the identity of a compound. Before we do this though. So how do we work out what the chemical is? In some cases. and HOW MUCH there is. There’s a difference. such as determining the difference between silver chloride and silver iodide precipitates. the intensity of the blue colour of a CuSO4 solution will increase as the CuSO4 becomes more concentrated. silver iodide is light green.

NH4+.       8   .ions) a desirable precipitate: • • • • has a known formula (so no variable water of hydration) does not react with atmosphere does not decompose under heating should generally have a high molar mass General steps in gravimetric analysis: • • • • Dissolve the sample in deionised/distilled water. ISO42OHCO32-. Dry/heat the precipitate and weigh it – repeat until constant mass. O2Solubility always soluble usually soluble usually soluble rarely soluble rarely soluble Exceptions* (except trivial ones) none (in scope of VCE) AgX (s). Filter the solution. NO3Cl-. Hence. the difference between chemicals we are exploiting is their solubility properties (qualitative) and we know that we can easily measure the amount of chemical by working out their mass (qualitative) as we can isolate the precipitate. we need to know what common kinds of ionic compounds precipitate.Thushan Hettige VCE Unit 3 Chemistry           WET-WAY ANALYSIS// 2. do we add CO32. GRAVIMETRIC ANALYSIS Here. PO43-. Add an excess of reagent that would form a precipitate.ions or NO3. Ion Group 1. S2-. The theme behind gravimetric analysis is this: the formation and weighing of a precipitate.ions or Cl. or treat the solution such as to isolate the ions of interest (for instance through filtration to get rid of insoluble impurities). Br-. and wash the precipitate with cold distilled/deionised water. PbX2(s) SrSO4 (s) BaSO4 (s) PbSO4 (s) Ba(OH)2 Notes HgI2 is also insoluble Ag2SO4 and CaSO4 are slightly soluble Ca(OH)2 is slightly soluble In choosing which precipitate to form (if we want to precipitate for instance Ag+ ions.

AOS 1 Test 1.Thushan Hettige VCE Unit 3 Chemistry           Worked Example 2. Dave dissolves this iron tablet in a beaker of distilled water. Question 1 modified) Dave wants to determine the percentage by mass of iron in a 0. Why does Dave have to repeat the drying and weighing steps? 1 mark       9   . a.1 (ATARnotes Chemistry Unit 3 Study Guide. Why is it optimal for the deionised water used for washing to be cold rather than hot? 1 mark Dave then dries the precipitate and weighs it. A barium sulphate precipitate is formed. 2 marks b. To this solution she adds a calculated excess of BaCl2 (aq).320 g iron tablet. She then proceeds to repeat this step multiple times until the mass obtained is constant. e. Why must the barium chloride be in excess? 1 mark Dave then filters out the precipitate and washes it with cold de-ionised water. Write a balanced ionic equation for the precipitation reaction (including states). The iron in the tablet is present as iron (II) sulphate – FeSO4. Why does Dave wash the precipitate with deionised water? 1 mark d. c.

Determine: the amount. of sulphate ions that have been precipitated ii. in moles. in grams. g. the mass. Explain why adding Ba(OH)2 instead of BaCl2 could lead to a higher amount of precipitate formed than when BaCl2 is used. 1 mark Total 11 marks       10   .Ba(OH)2 – with the rest of the procedure being the same. i. of iron in the iron tablet iii. repeats the experiment but instead decides to intentionally add an excess of barium hydroxide .Thushan Hettige VCE Unit 3 Chemistry           Dave finds the mass of precipitate to be 0. the percentage by mass of iron in the iron tablet 1 + 2 + 1 = 4 marks Another student. Pete. f.240 g.

HBr. NH3.       11   . In order to be able to tackle volumetric analysis. Cl. HCl/ClThe conjugate of a strong acid/base is a really bad base/acid (eg. and weak bases partially accept. HCl is a strong acid.is a horrible base and CH3O. SO42-. H3PO4. (eg. Strong bases accept protons from water to completion. F- An acid. becomes its conjugate acid. (eg. HI. Cl. CH3COO.is a weak base). pH = -log10[H+] pOH = -log10[OH-] pH + pOH = 14 Strong acids are acids that completely donate its protons to water. we need to have a sound understanding of acid-base chemistry. The basis of volumetric analysis is the titration. H2SO4. Characteristics of a primary standard: • • • • must have a known formula must have a relatively high molar mass must not react with the atmosphere should be soluble in water Examples of good primary standards are sodium carbonate and oxalic acid. HSO4CO32-. HF. The conjugate of a weak acid/base is a weak base/acid (eg. becomes its conjugate base. NH4+. when its proton is donated. However. Acid-Base Chemistry • • An acid is a proton donor.is a strong base. Weak acids partially donate. and CH3OH [methanol] is a horrible acid). how do we make up a known amount of stuff – a standard solution? We need a primary standard.Thushan Hettige VCE Unit 3 Chemistry           3.à HCl) A conjugate acid-base pair differs by one proton: eg. A base is a proton acceptor. HNO3 OHCH3COOH. where we want to determine amounts or concentrations of stuff by using known amounts of stuff. something that we can weigh and dissolve. Strong acid Strong base Weak acid Weak base Examples HCl. VOLUMETRIC ANALYSIS In volumetric analysis we are exploiting acid-base or redox properties (in general) of the different chemicals. when its proton is accepted. CH3COOH is a weak acid. HCl à Cl-) A base.

The relative proportions of the acid and conjugate base (and hence the colour) depend on the pH of the solution. So.       12   . and since we used a weak base. Acid-Base Titration Curves Let’s say we measure the pH of an aliquot of a basic solution. hence pH > 7. and conjugate base is a horrible base (as the acid was strong).+ H2O At equivalence point. salt is in solution. Strong acid – strong base eg. the conjugate acid is also a weak acid and this will be in solution.Thushan Hettige VCE Unit 3 Chemistry           Indicators are chemicals that allow you to see when the equivalence point has been reached.+ CH3COOH à H2O + CH3COOAt equivalence point. salt is in solution. indicator gives an indication (forgive the pun) of pH. OH. and since we used a weak acid. HCl + NH3 à NH4+ + ClAt equivalence point. hence pH < 7. Acid-base indicators are themselves weak acids/bases themselves where the acid form (say HA) has a distinctive colour from its conjugate base (say A-). hence pH = 7. only salt is in solution. the conjugate base will also be a weak base. Strong acid – weak base eg.à Cl. HCl + OH. where the equivalence point is 25 mL. Strong base – weak acid eg.

There may be indicators (eg. MnO4. She loads the HCl solution into a burette.305 g sample of sodium carbonate (Na2CO3).0 mL volumetric flask. which she quantitatively transfers into a 250. which has a concentration of approximately 0. She pipettes a 20. pipette small volume of base deionised water small volume of acid     small volume of base   deionised water 13   .1 M. so pH ~ 7.1 (ATARnotes Chemistry Unit 3 Study Guide. Redox Titrations The principles are the same here. starch for iodine) or one of the reagents can act as an indicator (eg.modified) Michelle wants to standardise a solution of HCl. This would NOT be a good titration to do. a. Circle the substance the following pieces of volumetric glassware should be washed with immediately prior to this experiment. Worked Example 3. we have a mixture of the conjugate base and acid (from weak acid and base). to which she makes up to the mark with distilled water.Thushan Hettige VCE Unit 3 Chemistry           Weak base – weak acid CH3COOH + NH3 à NH4+ + CH3COOAt equivalence point. burette small volume of acid ii. and explain why washing with the other alternatives is not optimal: i.which is intensely coloured). What is a standard solution? 1 mark She weighs a 1. Question 2 . AOS 1 Test 1. b.00 mL aliquot of the sodium carbonate solution into a conical flask.

d. in moles. Which of the following indicators is the most appropriate for the titration? Circle one answer and explain in the space below. the amount.57 mL. and obtains an average titre of 19. conical flask small volume of acid small volume of base deionised water 1 + 1 + 1 = 3 marks c. of sodium carbonate in the aliquot       14   . methyl red phenolphthalein 3 marks Michelle titrates the hydrochloric acid solution with the sodium carbonate solution.Thushan Hettige VCE Unit 3 Chemistry           iii. Calculate i.

Explain how leaving the funnel on the burette during the titration may increase or decrease the calculated concentration of HCl: 2 marks Total 13 marks       15   . the exact concentration of the HCl solution 2 + 2 = 4 marks e.Thushan Hettige VCE Unit 3 Chemistry           ii.

it is MUCH easier. as you are performing subtractions (where you monitor decimal places) as well as multiplication/divisions (where you monitor significant figures)!       16   .Thushan Hettige VCE Unit 3 Chemistry           Back Titrations This is a titration technique performed if (among other reasons): • • direct titration of the analyte with the standard solution implies a ‘strong-weak’ acid-base reaction and the product of the first reaction (see next set of dot points) can be expelled (for instance CO2 or NH3) The steps involved are: • • addition of a known amount of excess reactant to react with all of the analyte and expulsion of all reactive products (eg. Especially with back titrations. you MUST keep track of your accuracies (‘sig figs’) throughout the calculations. NH3) determination of the amount of reactant that has not reacted with the analyte through titration To solve these kind of problems. This way. it is essential to think through each step of the technique.

2 (VCAA 2008.Thushan Hettige VCE Unit 3 Chemistry           Worked Example 3. Question 8)       17   .

4. Balance all heteroatoms (not H or O).ions. Combining half equations: • Multiply each equation by the appropriate factor. 2.1 Derive an overall equation for the oxidation of Fe2+ to Fe3+ by MnO4.Thushan Hettige VCE Unit 3 Chemistry           4. so when you add the two equations the electrons cancel out. Don’t forget to cancel out any water or H+ on both sides! Worked Example 4. Balance charge by adding electrons. which themselves get reduced to Mn2+ ions. Worked Solution       18   . Balance O by adding H2O. 3. and you have your full equation. Balance H by adding H+. REDOX CHEMISTRY • • Oxidation is loss of electrons (or increase in oxidation number) Reduction is gain of electrons (or decrease in oxidation number) Writing redox half equations (we are going to assume that it’s in acidic solution): 1.

d. an invention. generally has +1. O = -2]) H. e. The sum of the oxidation numbers of each atom is equal to charge of species (eg.5). being very electropositive. b. The oxidation number system bases itself on the assumption that in a polar bond P—N (where N is more electronegative so the electron pair is closer to the N).2 Work out the oxidation numbers of the atom in brackets in the following species: a. FeCl3 (Fe) 3 NaOH (Na) 1 NO (N) 2 Cl2O (Cl) +1 K2O2 (O) -1       19   . Rules for oxidation numbers: • • • • • Oxidation number of an element is 0. being second most electronegative atom. both electrons ‘belong’ to the N. O = +2) F = -1 unless its F2 Worked Example 4. except peroxides (-1) and superoxides (-0. will be -2 . has -1 in hydrides when bonded with even more electropositive metals O. c. NO3[N = +5. OF2 (F even more electronegative.Thushan Hettige VCE Unit 3 Chemistry           Oxidation Number This is a tool. But it works.

Thin-layer chromatography is primarily a qualitative technique. It is quite versatile – it can be used for many compounds. Thin-layer chromatography// Of the chromatographic techniques you learn in Unit 3 Chemistry. The different types of chromatography we study are: • • • Thin-layer Chromatography (TLC) Gas Chromatography (GLC or GSC) High Performance Liquid Chromatography General Principles// • What determines the speed of the component through the stationary phase? Intermolecular bonding. the slower it will travel. dispersion forces.Thushan Hettige VCE Unit 3 Chemistry           5. The less soluble/more adsorbed to the stationary phase a substance is. Let us now have a look at each of the chromatographic methods in turn. dipole-dipole interactions. • • These principles apply to all of the following chromatographic methods.       20   . from drugs to amino acids. CHROMATOGRAPHY The main principle here is that we separate substances according to their interactions with the stationary phase and the mobile phase. but we cannot accurately determine their amount. using this technique we can identify compounds. this is the simplest and cheapest method. The stationary phase is the substance that remains ‘still’ throughout the analysis and the mobile phase is the substance that passes through/over the stationary phase. Consider hydrogen bonding. the faster it will travel. The more soluble/less adsorbed to the stationary phase a substance is.

The eluent starts to move up the plate. a second pencilled line drawn where the eluent line (the solvent front) was. The spotted samples on the pencilled lines MUST be above the line of eluent initially. how do we differentiate between compounds using TLC? We differentiate them by how fast they travel up the column. the plate is removed from solution.0 cm. the greater the affinity of the compound for the mobile phase and the less the adsorption of the compound to the stationary phase. and after the development of the chromatogram we have the solvent front travelling a distance of 5. the eluent. Why cannot we definitively say that this compound is paracetamol?       21   . paracetamol has an Rf value the same as that calculated in this experiment. carrying the sample with it. and the substance travelling 3. the stationary phase and temperature. Now.0 cm.Thushan Hettige VCE Unit 3 Chemistry           The setup is as follows (apologise for the lack of artistry here!): Setup card coated with alumina or silica (stationary phase) spots of sample to be analysed A   B   C   D   E   To prepare a TLC. the faster the compound will travel through the column. The card is then placed in a cylindrical container containing eluent – the solvent that acts as the mobile phase. What is the Rf value? It is found that. we use a capillary tube to ‘spot’ tiny samples of each compound to be analysed on a pencilled line on the card. It is calculated as follows: Rf = component/solvent. Remember. and the spots on the TLC plate observed under visible or UV light. suppose that we perform a TLC on an unknown compound. otherwise the samples will dissolve into the eluent instead of moving up the plate. After the eluent has moved up the plate a sufficient distance. in previous experiments. ratio of distances travelled by the solvent and the component. Note that Rf value depends on the compound. This means that it is possible that this compound is paracetamol. The measurement for how fast the compound travels through the column is the retardation factor (Rf) value. How do we use this Rf value? Well.

Question 3b)       22   . remember that like dissolves like. This means that polar substances tend to adsorb onto the polar stationary phase to a greater degree and non-polar substance tend to dissolve into the mobile phase better. using these general principles.Thushan Hettige VCE Unit 3 Chemistry           Polarity of Stationary and Mobile Phases Often. the stationary phase is a polar substance such as silica or alumina and the mobile phase (eluent) is a non-polar organic solvent such as ethyl ethanoate. Therefore. Now. which substance will travel further up the plate – the polar or non-polar substances? Worked Example (VCAA 2008.

we measured how fast the sample goes up the plate by measuring the retardation factor. the higher or lower the retention time?       23   . In TLC. eluent added on top of the sample. the stronger the intermolecular forces between the silica and the sample (and the weaker the intermolecular bonds between the eluent and the sample). Just like in TLC. carrying the sample with it. Again. This is called the retention time. The sample is pipetted onto the packed silica column. and the tap opened. In column chromatographic methods though. Question: the stronger the intermolecular bonds between the sample and the stationary phase.Thushan Hettige VCE Unit 3 Chemistry           Column Chromatographic Methods Before we embark on the other two chromatographic methods – HPLC and GC – let us explore the simple setup of column chromatography: This column is like a burette without markings. a ratio of distances travelled by the eluent and the sample. we measure the time taken for the sample to travel through the column. The eluent is allowed to go through the column and drip out of the burette. the sample will adsorb onto and desorb from the silica. the slower the sample goes through the column.

This means that the more adsorptive components of the sample will separate better from the less adsorptive. except that it is mechanised. Gas Chromatography Gas chromatography is another form of column chromatography. saving time. As a method of column chromatography. N2) the sample is in the gaseous phase   24   • •     . There’s a downside to this though. then passing water through a column packed with sand. We can actually collect the fractions of sample as it comes out of the column and perform analyses that will test for their amount. we are doing this already: it’s called high performance liquid chromatography (HPLC). it would make sense if we could use extremely fine pieces of silica to increase separation – but hand pumps would not be able to pressurise the eluent to 14000 kPa (about 140 atmospheres of pressure). You’d rather use finer pieces of silica than coarse – because there is a higher surface area of silica with which the sample can potentially adsorb. How about using a hand-pump to pump the eluent under pressure through the column? This will make the eluent pass through the column faster.000 kPa through a really robust column able to withstand such pressures – and use an electronic detector to measure how much of each compound in the sample is passed through the column? Well. it is the most accurate and sensitive of chromatographic techniques – and the most expensive. there is a way to get around this. one thing. Gas chromatography is somewhat unusual in that: • the stationary phase is either a solid (eg. imagine trying to pass water through a column packed with big gravel pieces. Now. using finer pieces of silica has the same effect as using a longer column. The stationary phase is generally alumina or silica. wouldn’t it? It is also said that time is money – so time is valuable. The water will pass much more slowly through the sand. and the mobile phase generally a nonpolar organic solvent. However.Thushan Hettige VCE Unit 3 Chemistry           The difference between this and TLC is that this method allows for quantitative analysis of the samples. therefore using finer pieces of silica has a downside to it – it takes longer. alumina in gas-solid chromatography) or a liquid (high boiling point hydrocarbon or ester in gas-liquid chromatography) coated on a porous solid the mobile phase (eluent) is an inert gas (eg. the Rt value is used to identify compounds. How to interpret HPLC chromatograms will be discussed later. H2. High Performance Liquid Chromatography High performance liquid chromatography is effectively identical to the basic form of column chromatography. How about if we use a really powerful machine to pump the eluent at 14. Even then though.

The area under the peak that the compound gives rise to gives information about the amount of that compound. With this calibration curve. We can plot a calibration curve by taking samples of the compound of known amount and determining the area under the peak at its retention time.000 square units. However. It is found that. we can tell what amount of compound that corresponds to. it is not valid to use that curve to determine the amount of compound in that sample.       25   .Thushan Hettige VCE Unit 3 Chemistry           Given that the states of the stationary and mobile phases are different. Another note: calibration graphs cannot be extrapolated accurately. or 0. This means that there are no intermolecular bonds between the sample and the mobile phase. monosaccharides and amino acids) also cannot be analysed as attempting to vaporise them in the oven will make them decompose • Analysing chromatograms for GC and HPLC The chromatograms for GC and HPLC have identical features. the general rule is if the molar mass is > 300 g mol-1 the compound cannot be detected compounds that decompose at high temperatures (eg. suppose we are trying to separate a mixture of straight-chain alkanes using gas-liquid chromatography where the stationary phase is a high boiling point hydrocarbon. at low amounts. we now know a relationship between the area under the peak and the amount of compound – and therefore when we measure the area under the peak of an unknown amount of compound to be 12. or 2 mol. we need to consider our intermolecular bonding a little differently. how do we know what amount corresponds to what area? If I get an area of 12. So. This means that we can only consider intermolecular forces between the stationary phase and the sample.1 mol? This is where calibration curves come in. the area under the peak is proportional to the amount of compound. therefore.000 square units. Consider the following examples of a chromatogram (on page 27): Remember that the retention time identifies the compound. Which alkane will have the greatest retention time? The fact that the sample has to be in the gaseous phase in the column raises two points: • compounds that are not easily vaporised – they don’t have a low boiling point – cannot be detected using gas chromatography. if the area under the peak of an unknown amount is outside the range of the calibration curve. Recall from Unit 2 Chemistry that the ideal gas law (pV = nRT) is based on the assumption that there are no intermolecular bonds between gas molecules. the location of the peak identifies the compound. how do I know whether that corresponds to 1 mol.

Thushan Hettige VCE Unit 3 Chemistry           Worked Example (VCAA 2011. Question 3)       26   .

Thushan Hettige VCE Unit 3 Chemistry                 27   .

Thushan Hettige VCE Unit 3 Chemistry                 28   .

This electron will be at an unstable position. In doing so. Below is a table of different types of light that is used in spectroscopy. this electron emits a light particle (a photon) of a specific energy. It follows that if an electron in an atom can emit a photon of light of a particular energy (hence frequency/wavelength) in going down from its unstable energy level to its stable energy level. measured in Hz.Thushan Hettige VCE Unit 3 Chemistry           6. we can turn our attention to AAS and UV-visible spectroscopy. hence a specific frequency/wavelength. spectroscopy does it by their different patterns of absorption of electromagnetic radiation. that same electron can emit a photon of the same energy (hence frequency/wavelength) in going from its stable energy level to its unstable energy level. High Wavelength High . so will immediately drop down to its stable low energy level. SPECTROSCOPY (AAS + UV-VIS) Just as chromatography differentiated between compounds by their relative attractions to the stationary and mobile phases. Atomic Absorption Spectroscopy An electron in an atom can be excited to a higher shell – a higher energy level. from low to high frequency: Frequency Low . Electromagnetic radiation One way of looking at light is that light travels as particles of a particular frequency. .       29   . but they should be recognised: • • the frequency of the light ‘particle’ is proportional to the energy of the photon the wavelength of the light ‘particle’ is inversely proportional to the frequency of the particle – hence the wavelength is inversely proportional to the energy Now that we have an understanding of electromagnetic radiation. Low Type of Radiation Radio Infra-red Visible Ultraviolet Spectroscopy in which it is used NMR IR AAS/UV-visible AAS/UV-visible Here are a few points to notes – these need not necessarily be memorised. as it is better to cover these in conjunction with organic chemistry. Note that this section will cover atomic absorption spectroscopy and UV-visible spectroscopy only. Infra-red and nuclear magnetic resonance spectroscopies – and mass spectrometry – will be covered in the AOS 2 section (although they are AOS 1 material). .

the lower its energy. The gaseous metal atoms floating in the flame will absorb the light shot at them from the lamp monochromator/detector – select wavelengths of light and detect light. Hence. if we sprayed a sample of NaCl (aq) into this flame. we need to work out how this pattern of light absorption is different between atoms and why this pattern is different. and the energies of those electrons will be higher (electrons become more distant from nucleus). and therefore will absorb photons of specific different energies hence frequencies/wavelengths. only a few of the emitted photons from the lamp will happen to hit the atoms and be absorbed – most will go through. Why? atomiser – this is composed of a flame (fyi its due to combustion of C2H2) which turns the metal ion sample into the gaseous state and reduces the metal ion to the element. If there are a lot of gaseous atoms in the flame. the resulting species of interest will be Na (g) [not Na+ (g)]. if there are only a few gaseous metal atoms floating in the flame. The setup is as follows: The components of the atomic absorption spectrometer are: • cathode ray lamp – this is a lamp containing a small amount of the metal of interest (there is a Na lamp.       30   . The electrons in the metal in the lamp are excited by a voltage and when they go back down to their stable energy levels.Thushan Hettige VCE Unit 3 Chemistry           How can we exploit this property to differentiate between different atoms? To do so. • • Now. but too many electrons in the same shell means there is more repulsion between electrons in the same shell. for instance. they emit light – which is shot at the sample to be analysed. So. Note that the closer an electron is to the nucleus. It turns out that (put simply) different atoms will have different differences in energies between electron shells. Not too important to know the mechanisms of their function here. The awesome thing about this is that all of the light emitted will be absorbed by the metal of interest and only the metal of interest. This is because different elements have a different electronic configuration and nuclear charge. we can exploit this and find the relationship between the amount of light absorbed (absorbance) and the concentration of the metal ion (in the sample that is sprayed onto the flame). A higher nuclear charge brings all the electron shells closer to the nucleus (and therefore perhaps closer to each other as well). more of the emitted photons will happen to hit the metal atoms and be absorbed – less light will go through. a K lamp. and so on).

we need a UV-visible spectrum. UV-Visible Spectroscopy Put simply. absorbance and concentration of metal ion is proportional.Thushan Hettige VCE Unit 3 Chemistry           It turns out that for low concentrations. The main difference is that you choose the wavelength to be absorbed (unlike in AAS). Therefore. you need to determine the most appropriate wavelength of light to be absorbed. otherwise it will interfere with the measurement of the compound to be analysed In order to select the right wavelength. UV-visible spectroscopy exploits bonding electrons in molecules being excited to higher energy levels. This wavelength must satisfy the following conditions: • • the compound to be analysed must absorb quite strongly at that wavelength no other compound that could be in the sample can absorb well at that wavelength. The principles of UV-visible spectroscopy are effectively the same – and so is the setup. just as AAS exploits electrons in atoms being excited to higher energy levels. The exact nature of the energy levels in bonding electrons in molecules is well beyond the scope of the course. like the one below: Consider the following question – VCAA 2010 Question 9       31   .

and the amount of light absorbed measured (again. We can get samples of known concentration and run them through the AAS or UV-Visible spectrometer and get their absorbances at the specific wavelength. Then we can run our actual sample through the AAS or UV-visible spectrometer and get its absorbance at the wavelength. How did we combat those? We used calibration curves. a small clear cuboidal container). and use the calibration line to work out the concentration of the compound. and then draw a calibration curve plotting these points. It also turns out that absorbance and concentration of the compound are proportional at low concentrations of compound. Again. remember that absorbance and concentration of compound are proportional – just like in GC and HPLC.Thushan Hettige VCE Unit 3 Chemistry           The mechanics are effectively the same. more light will be absorbed as more photons will hit the molecules and be absorbed.       32   . how does this translate into a concentration of compound in the sample? Well. Light of a specific wavelength is shone through the sample (which is stored in a cuvette. one cannot extrapolate outside the range of the calibration curve accurately. Like in the calibration curves in HPLC and GC. if we are given the absorbance of a solution at a particular wavelength. measured in absorbance). We can do it again here. Determining concentrations of compound using AAS and UV-Vis Again. and the light remaining is detected. if there is a high concentration of compound.

Question 2)       33   .Thushan Hettige VCE Unit 3 Chemistry           Worked Example (VCAA 2008.

Thushan Hettige VCE Unit 3 Chemistry           END OF AOS 1       34   .