University Of Central Lancashire Department of Forensic and Investigative Science FZ1025 Experimental Techniques in Chemistry

10 Functional group analysis

INTRODUCTION This investigation consists of three sections: 1) You are going to illustrate qualitative analytical tests for the presence of specific Functional Groups in organic compounds. 2) You are going to analyse the Infra red spectra of five unknown compounds A, B, C, D, and E to attempt to identify the functional group present in each. (Each compound will only possess a single functional group). 3) You are going to carry out qualitative analytical tests to confirm the identity of the functional groups present in the five unknown compounds.

The functional groups under investigation are:

H C R C H R H O C R R C H O

Alkene

Ketone

Aldehyde

O R C OH R H2 C OH

Carboxylic acid

Primary alcohol

Where R represents hydrocarbon group or carbon skeleton.

PRE-LAB QUESTIONS 1) In terms of both wavelength and frequency where is the infra-red region of the electromagnetic spectrum that is used in most laboratory infra-red spectrometers? (3 marks) 2) What happens to the bonds in a molecule when the absorb IR radiation? (2 marks)

3) A C-O stretch appears in the region 1260-1000 cm-1 and the C=O stretch appears between 1760 and 1670 cm-1. Why is the C=O at a higher wavenumber even though they are both carbon-oxygen bonds? If C-O was changed to C-S would the peak be shifted to a higher or lower wavenumber? (5 marks)

HEALTH & SAFETY Chemical / Process Hazard Severity Grade 1-4 A

2 2 2 2 2

Likelihood of occurrence Grade 1-4 B

2 1 2 2 2

Risk (A x B) (Likelihood x hazard)

4 2 4 4 4

Safety

Hexene Citric acid Butane-2-one Butanal 1-Butanol

Bromine water

Sodium carbonate 2,4-dinitrophenyl hydrazine Methanol

1 2

1 2

1 4

Sulphuric acid

Sodium hydroxide, 2 -1 mol L Silver nitrate, 0.1 mol -1 L Ammonia solution, 2 -1 mol L Potassium

1 1 2

2 2 2

2 2 4

Highly flammable. Wash with copious amounts of water. Irritant, may cause serious damage to eyes. Highly flammable, irritating to eyes. Wash with copious amounts of water. Highly flammable, irritating to eyes. Wash with copious amounts of water. Harmful if swallowed, flammable, irritating to eyes. Wash with copious amounts of water. Toxic by inhalation, causes burns. Wear gloves and wash with copious amounts of water. Irritating. Wash with copious amounts of water. Explosive when dry, harmful. Wash with copious amounts of water and consult a physician. Highly flammable, toxic. Wash with copious amounts of water and consult a physician. Corrosive, causes burns. Wash with copious amounts of water and consult a physician. Corrosive. Wash with copious amounts of water. Irritant. Wash with copious amounts of water. Flammable, toxic, causes burns. Wear gloves. Wash with copious amounts of water. May cause cancer. Wash with

dichromate, 0.1 mol -1 L Unknown samples

copious amounts of water and consult a physician. Treat with utmost respect; assume toxic, corrosive. Wear gloves.

EXPERIMENTAL 1 Qualitative Analysis The following exercise will give you a positive result for each analytical test. Make full and detailed observations of the outcomes, recording your findings in a table.

a) Reaction with Bromine Water (care corrosive, Irritant) To 2 drops of hexene (flammable), in a test-tube, add a few drops of bromine water. Shake and record any colour change. b) Reaction with aqueous Sodium Carbonate Add a small amount of solid citric acid (sufficient to just cover the end of a spatula) to 5% aqueous sodium carbonate solution (about 1 cm 3) in a test-tube and report any changes that occur. c) Reaction with Bradys Reagent (2,4-dinitrophenylhydrazine in methanol and sulphuric acid) (corrosive) Working in a fume cupboard, carefully add 2 drops of butanone to 1 cm3 of Bradys reagent contained in a test tube. If there is no immediate reaction, cool the test-tube in an ice bath and gently, with care, scratch the inside of the test-tube with a glass rod. d) Reaction with Tollens Reagent [Ag(NH3)2]+ (aq) Tollens reagent must be prepared immediately prior to use as follows: Add two drops of 2 mol dm-3 solution of sodium hydroxide (irritant) to 2cm3 of a solution of 0.1 mol dm-3 silver nitrate contained in a boiling tube, this should form a brown precipitate (Ag 2O). Then drop-wise add an ammonia solution (irritant, harmful) until the initial precipitate just redissolves. Prepare a boiling tube containing Tollens reagent. Add 2 drops of butanal (irritant). Carefully place the boiling tube in a warm water bath (~50 0C) consisting of a 600 cm3 beaker containing ~200 cm3 of water heated on a hot plate. Observe any changes that take place and report them in a table.

Silver ions (Ag+) are weak oxidising agents being reduced to silver metal and should only react with any functional groups that can be very easily oxidised. However, if there are any oxidisable impurities present a false positive test may result. e) Reaction with acidified potassium dichromate solution Prepare a mixture of 10 cm3 of 0.1M potassium dichromate solution (harmful) and an equal volume of dilute sulphuric acid (corrosive). Pour out about 2 cm3 of the acidified dichromate solution into a boiling tube, and add 2 drops of 1-butanol (flammable) to the solution. Heat gently over a low Bunsen flame and keep the tube moving gently in a sloping position, with the open end pointing away from you or other people. Boil gently and observe for any colour changes. Record your observations from these tests in a table Chemical Hexene Functional Test Group Reagent Alkene Bromine water Observation

Citric Acid

Carboxylic Acid

Sodium Carbonate (aq) Bradys Reagent

Butanone

Ketone

Butanal

Aldehyde

Tollens Reagent

Butan-1-ol

Alcohol

Acidified potassium dichromate (aq)

2 Infra Red spectroscopy analysis of unknowns

Identify the functional group present in each compound. Compound A

Compound B

Compound C

Compound D

Compound E

Table of IR absorption bands

Bond C-H C-H C-H C-O C=O C=C O-H O-H Carboxylic acids 3000-2500 (b) stretch (s) = Strong, (v) = Variable, (m) = Medium, (w) = Weak, (b) = Broad Aldehydes, Ethers, Carboxylic acids, Esters Alkenes Hydrogen bonded in Alcohols, Phenols 1760-1670 1680-1640 3600-3200 (s) stretch (m,w)) stretch (b) stretch Alkanes Alkenes Aldehydes Alcohols, Ethers, Carboxylic acids, Esters Functional Group Absorption -1 cm 1470-1350 2960-2850 3080-3020 1000-675 2650 - 2750 1260-1000 Characteristics (s) stretch (v) bending (m)stretch (s) bend (m) stretch (s) stretch

3 Qualitative analysis of unknown compounds For each of the unknowns to be tested use 2 drops if it's a liquid or just enough solid to just cover the end of a spatula. You are provided with samples of the five unknown compounds labelled A, B, C, D, and E. In the light of your analysis of the IR spectra of the unknowns, carry out a qualitative analytical test as detailed in part 1 of this assignment to confirm the identity of the unknowns. Unknown Compound
A B etc

Functional Group

Test Carried Out

Observations

POST-LAB QUESTIONS:
1. In your write up explain the chemical reactions behind the analytical tests carried out, including the use of equations. 2. Comment on the reliability of qualitative analytical tests.