Chemistry Lab Report 06 Name : Class : Class No : Date :

Title Objective : A practical study of some group elements : To study some of the properties of the elements of Group

Lam Wai Oi 7S 04 17th Dec, 07

and their compounds. Theory :

The s-block of the periodic table contains the most reactive and, in chemical terms, the most typically metallic elements. All the elements in Group are highly reactive, but those in Group are slightly less so and show a rather more obvious trend in reactivity. Procedure A. 1. 2. 3. 4. :

Reaction of the elements with water Put a small piece of calcium metal into a large beaker of cold water. Observed the reaction and identify the products. Repeated step 1 and 2 by using a small piece of clean magnesium ribbon and then barium metal. The reaction of magnesium with water was very slow. Investigated the reaction further by setting up the experiment shown in figure.

B.

Acid-base character 1. Placed about 0.01g of magnesium oxide, calcium hydroxide and barium hydroxide in three separate test tubes. Added 10cm3 distilled water to each tube and shake. Added 2 drops of universal indicator solution to each tube and mix. 4. Recorded the pH values indicated for the three tubes. Strongly heated about 1cm depth of each of the hydrated chlorides of magnesium, calcium and barium in separate, dry hard-glass test tubes in the fume cupboard. 2. Tested for the evolution of hydrogen chloride.

2.
3.

C.

Hydrolysis of the chlorides 1.

D.

Thermal stability of the carbonates 1. Strongly heated about 1cm depth of each of the dry carbonates of magnesium, calcium and barium separately in the apparatus shown in figure. 2. 3. 4. Noted how rapidly gas is evolved, and the extent to which the lime-water becomes milky. Removed the tube from the lime-water before heating has stopped. Recorded the time that lime-water became milky. Put 2cm3 of a 0.1M solution of magnesium chloride, calcium chloride and barium chloride under investigation in separate test tubes.

E.

Solubility of some compounds of Group elements

1.

2. 3. 4.

Added an equal volume of a 1.0M solution of sodium hydroxides, and mix. Noted whether a precipitate was formed, if so, how dense it was. Repeated the experiment twice, using first a 1.0M solution of sodium sulphate and then a 1.0M solution of sodium carbonate, instead of the sodium hydroxide.

Results A.

: Solution changed became milky -

Reaction of the elements with water Element Fume produced Gases evolved s Ca(s) white colourless Mg(s) Mg(powder) pH value 7 10 10

B.

Acid-base character Elements MgO Ca(OH)2 Ba(OH)2

C.

Hydrolysis of the chlorides Elements Had gas evolved or not MgCl2 CaCl2 BaCl2 No No No

D.

Thermal stability of the carbonates

Elements MgCO3 CaCO3 BaCO3

Time of lime-water turned to milky 55s 97s -

E.

Solubility of some compounds of Group elements Elements Mg2+ Ca2+ OHTranslucent solid occurred No observation Translucent precipitate on the above : White precipitate occurred, small colourless layer on the above White precipitate occurred, colourless layer on the above Had white solid

Ba2+ Little amount of translucent precipitate occurred Had white precipitate Large amount of white precipitate occurred

SO42CO32-

Discussion A.

Reaction of the elements with water Those two metals, calcium and magnesium react with water theoretically. Ca(s) + 2H2O(l) Ca(OH)2(aq) + H2(g) Mg(s) + H2O(l) MgO(s) + H2(g) However, even reacted with hot water, magnesium had no observable changes in the reaction. The reaction may undergo too slow. But

calcium reacted with water readily and gave large amount of white fume. This indicates that calcium is more reactive than magnesium. In this experience, calcium and magnesium acted as reducing agents. The hydrogen ions in water were reduced by the Group elements B. became hydrogen gas.

Acid-base character Hydrolysis of the chlorides Thermal stability of the carbonates Solubility of some compounds of Group elements

C.
D.

E.

Reference : http://tonny.earthppl.com/att/Chemistry%20Report%205.doc http://www.rod.beavon.clara.net/bromobutane_prep.htm http://chemistry.csudh.edu/faculty/jim/Preparation%20of %201-bromobutane.doc

http://www.miracosta.cc.ca.us/home/dlr/210exp8.htm

http://tonny.earthppl.com/att/Chemistry%20Report%205.doc In the experiment, 1-bromobutane was synthesized through the second order mechanism in the present of concentrated sulphuric acid and sodium bromide. The nucleophile in the experiment is bromide ion (Br-) while the leaving group is water. Purification of the product was then obtained by extraction. The principle of extraction as a purification method was based on the difference in solubility between impurities and product. The functional group inter-conversion of an alcohol into alkyl halide takes place by a nucleophilic substitution reaction. In the experiment, the alkyl group was substituted on the primary carbon, the reaction proceeds by an SN2 mechanism. The primary alcohol, 1-butanol, was reacted with a mixture of sodium bromide and the concentrated sulfuric acid and hooked up to a water-cooled reflux condenser. The hydroxyl group of the 1-butanol was protonated by the sulphuric acid. Addition of the strong acid formed an oxonium ion from the 1 alcohol OH group, changing a poor leaving group (-OH) into a good one (H-O-H). The nucleophile, bromide, attacked the primary carbon and water was released, forming 1-bromobutane. The water that produced was then protonated, forming hydronium ion.

1-butanol

sulfuric acid

protonated alcohol

When sulphuric acid was added into the reaction mixture, cooling by means of an ice bath was needed. The apparatus must also be swirled at the same time to ensure the acid had reacted. This was to prevent the sulphuric acid from reacting too fast, as it was an exothermic reaction, and might run away splashing the acid everywhere if the reaction went too fast. Also the increased temperature might vaporise more quickly the 1-butanol, which would decrease the yield. Also, hot sulphuric acid would cause significant oxidation of the sodium bromide to bromine, which is useless in this experiment. The yield of 1-bromobutane could therefore be affected adversely.

The need for reflux was because the reaction needed to go to completion, and as with organic liquids it was often necessary to reflux because heat needed to be applied to the reaction without loosing reactants through evaporation. The reason for the multiple layers of products was that there were, several side reactions taking place at the same time in the flask, they are the drawbacks to using sulphuric acid. The acid could cause reactions such as the dehydration of alcohols and/or ether formation to occur which lower the yields of the alkyl bromides. (I) Sodium bromide reacted with sulphuric acid to form hydrogen bromide and sodium hydrogen sulphate. NaBr + H2SO4 HBr + NaHSO4 (II) Hydrogen bromide was oxidised to bromine molecules as concentrated sulphuric acid was a very good oxidising agent. The sulphuric acid reacted to form sulphur dioxide gas. HBr + H2 SO4Br2 + 2SO2 (g) (III) Hydrogen bromide dissociated and the bromide ion from it attacked the carbon atom with the -OH function group in 1-butanol and displaced the -OH function group forming a bromo function group and a hydroxide ion, which then associated itself with another H3O+ ion to form water. CH3CH2CH2CH2OH + Br- CH3CH3CH2CH2Br + OH-

(IV) A molecule of sulphuric acid attacked the lone pair on an -OH function group, releasing a molecule of water, and a mixture of butoxybutane and but-1-ene was formed, along with the regenerated sulphuric acid. CH3CH2CH2CH2OH + H2SO4 CH3CH2CH=CH2 + H2O + H2SO4 2 CH3CH3CH2CH2OH + H2SO4 CH3(CH2)3O(CH2)3CH3 + H2O + H2SO4 To identify the organic layer in the separatory funnel, carefully draw off about 0.25 mL of the lower layer into a test tube containing about 1 mL of water and mix vigorously. If the liquid from the funnel dissolves in the water as you mix it, the lower layer is aqueous.

1-butanol went through an SN2 reaction by using sodium bromide in water to create hydrobromic acid in the presence of excess sulfuric acid. Thus, water was the leaving group and bromide ion was the nucleophile in this in situ reaction. This displaced the alcohols -OH group with a bromine creating 1-bromobutane. The excess sulfuric acid pushed the reaction far to the right corresponding with LeChatliers principle which states that more reactants yield more products. The extractions further isolated the product, the substance which has higher density was always the bottom layer and the lighter was on top. It turned out that the organic layer was always on the bottom of each extraction. Anhydrous magnesium sulphate was a very good drying solution. This allowed it to soak up the remaining water to a great extent. This reaction must be a SN2 reaction as the product was almost entirely 1bromobutane, if by an SN1 mechanism, the product should consist of mostly 2bromobutane derived from the sec-butyl cation formed via a 1,2-hydride shift.

Such an interpretation of the product distribution must be made with caution. The presence of small amounts of 2-bromobutane in the reaction product did not necessarily mean that it was produced from 1-butanol via an SN1 mechanism because an alternative sequence of an E2 elimination of the protonated 1-butanol to give 1butene followed by HBr addition to the 1-butene would also produce 2-bromobutane.

Precautions were taken to prevent the highly inflammable and volatile alcohol from catching fire or lost through evaporation. The pressure of the separatory funnel must be periodically released to avoid the stopper being pushed out and product being lost and sprayed. The pressure is due to

liberated carbon dioxide.

http://www.rod.beavon.clara.net/bromobutane_prep.htm

Why is the sulphuric acid added slowly, and why is cooling and shaking needed? Sulphuric acid when diluted with water gives out a great deal of heat, enough sometimes to raise steam which would cause dangerous splashing. Also, hot 50% sulphuric acid (which is what is produced in the flask) will cause significant oxidation of the sodium bromide to bromine, which is useless in this experiment. The yield of 1-bromobutane could therefore be affected adversely. Why is a sand-bath used for heating? The sand spreads the heating uniformly over the base of the flask. This reduces the likelihood of cracking, and of unwanted side reactions occurring (e.g. excessive oxidation either of bromide ions to bromine or of the alcohol to carbon) owing to hot-spots. Why is the mixture heated for 45 minutes? Most organic reactions are slow because of the need to break strong covalent bonds. Why is the mixture distilled at this stage? The liquid 1-bromobutane is removed from the involatile sodium salts (mostly sodium hydrogen sulphate at the end of the reaction) and the much less volatile sulphuric acid. The 1bromobutane will be contaminated with water, unchanged butan-1-ol, and some sulphuric acid carried over as tiny droplets during the distillation. What does shaking with water achieve? Water will remove sulphuric acid and some of the butan-1-ol. How do you decide which layer is to be kept? On the basis of density; 1-bromobutane has a density of 1.276 g cm-3. Why is concentrated hydrochloric acid added? The acid protonates the butan-1-ol, giving an ionic species that is much more soluble in water than the alcohol itself: CH3CH2CH2CH2OH + H+ CH3CH2CH2CH2OH2+

Why is the mixture shaken with sodium carbonate solution? This removes hydrochloric acid dissolved in the 1bromobutane: Na2CO3 + 2HCl 2NaCl + CO2 + H2O

Why must the pressure be periodically released? To avoid the stopper being pushed out and product being lost and sprayed all over you. The pressure is due to liberated carbon dioxide. What is the function of the calcium chloride? Calcium chloride is a drying agent. What if the mixture isn't clear? Then it is not dry; the cloudiness is caused by tiny droplets of water in the 1-bromobutane.

http://chemistry.csudh.edu/faculty/jim/Preparation%20of%201-bromobutane.doc The overall reaction is: H2SO4 + NaBr + CH3CH2CH2CH2OH 6 CH3CH2CH2CH2Br + H2O + NaHSO4

http://www.miracosta.cc.ca.us/home/dlr/210exp8.htm As you learned in lecture, this general class of reactions requires three things: a nucleophile, an electrophile, and a leaving group. In order for the reaction to proceed via the SN2 mechanism, the nucleophile should be in the "good" to "excellent" range, the electrophile must be unhindered (methyl or 1), and the leaving group should also be in the "good" to "excellent" range.

CH3CH2CH2CH2-OH2+ + Br-

CH CH CH CH -Br + H O
3 2 2 2 2

we see that the first two are satisfied (bromide is an excellent nucleophile and the electrophile is a 1 alkyl group), but hydroxide is a poor leaving group, due to its negative charge and its high basicity. The central question becomes, "how can we make OH- into a better leaving group? We have a few choices: 1) react the alcohol with p-toluenesulfonyl chloride (abbreviated TsCl), which will convert the OH group into a sulfonic acid ester, making it a much better leaving group--then react the ester with sodium bromide to produce 1-bromobutane; 2) react the alcohol with phosphorus tribromide (PBr3), which converts the OH into a "P(OH)X2" leaving group (where X is either Br or OH), and which also produces free bromide ions which react with the electrophile, replacing the new leaving group, all in one reaction mixture; or 3) using a strong acid to protonate the OH group in the presence of the bromide ion, which changes the leaving group from hydroxide to water, and allows the bromide to react with it in the same mixture.