The carbonates and nitrates of group 2 elements carbonates become more thermally stable as you go down the Group. 1. The reason, once more, is that the polarising power of the M2+decreases as ionic radius increases. For nitrates we notice the same trend. Don't waste your time looking at it. Both carbonates and nitrates of Group 2 elements become more thermally stable down the group. It has a high charge density and will have a marked distorting effect on any negative ions which happen to be near it. You have to supply increasing amounts of heat energy to make them decompose. b) lower c) A white solid producing a brown gas and leaving a white solid. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. Thermolysis of 2-methyl-2-butanol nitrate in diethyl ether over a Brown nitrogen dioxide gas is given off together with oxygen. Brown nitrogen dioxide gas is given off together with oxygen. The carbonate ion becomes polarised. For the sake of argument, suppose that the carbonate ion radius was 0.3 nm. The explanation for change in thermal stability is the same as for carbonates Magnesium nitrate decomposes the easiest because the Mg 2+ ion is smallest and has the greater charge density. XCO_{3(s)} \longrightarrow XO_{(s)} + CO_{2(g)}, 2X(NO_3)_{2(s)} \longrightarrow 2XO_{(s)} + 4NO_{2(g)} + O_{2(g)}, \begin{gathered} Brown nitrogen dioxide gas is given off together with oxygen. Brown nitrogen dioxide gas is given off together with oxygen. How much you need to heat the carbonate before that happens depends on how polarised the ion was. For the purposes of this topic, you don't need to understand how this bonding has come about. The nitrates also become more stable to heat as you go down the Group. GROUP 2: THERMAL STABILITY OF THE CARBONATES AND NITRATES 1. a) Both barium carbonate and barium oxide (the product) are white. This is a rather more complicated version of the bonding you might have come across in benzene or in ions like ethanoate. Strontium Nitrate Strontium has a greater ionic radius than beryllium since it is affected by more electrostatic forces of attraction due to more protons in its nucleus and more electron shells. The rates at which the two lattice energies fall as you go down the Group depends on the percentage change as you go from one compound to the next. For reasons we will look at shortly, the lattice enthalpies of both the oxides and carbonates fall as you go down the Group. For example, for magnesium oxide, it is the heat needed to carry out 1 mole of this change: Note: In that case, the lattice enthalpy for magnesium oxide would be -3889 kJ mol-1. The nitrate ion is bigger than an oxide ion, and so its radius tends to dominate the inter-ionic distance. In group 1 and 2, the nitrates and carbonates get more stable down the group. On that basis, the oxide lattice enthalpies are bound to fall faster than those of the carbonates. All the carbonates in this Group undergo thermal decomposition to give the metal oxide and carbon dioxide gas. (You wouldn't see the oxygen also produced). THERMAL STABILITY OF THE GROUP 2 CARBONATES AND NITRATES. Here's where things start to get difficult! All of these carbonates are white solids, and the oxides that are produced are also white solids. You need to find out which of these your examiners are likely to expect from you so that you don't get involved in more difficult things than you actually need. Due to the large size of the sulphate anion there is little difference betw… if you constructed a cycle like that further up the page, the same arguments would apply. Confusingly, there are two ways of defining lattice enthalpy. I can't find a value for the radius of a carbonate ion, and so can't use real figures. You can dig around to find the underlying causes of the increasingly endothermic changes as you go down the Group by drawing an enthalpy cycle involving the lattice enthalpies of the metal carbonates and the metal oxides. Exactly the same arguments apply to the nitrates. It has been The lattice enthalpy of the oxide will again fall faster than the nitrate. For the purposes of this topic, you don't need to understand how this bonding has come about. Explaining the trend in terms of the energetics of the process. If "X" represents any one of the elements: As you go down the Group, the carbonates have to be heated more strongly before they will decompose. The ones lower down have to be heated more strongly than those at the top before they will decompose. One of the products of lithium nitrate's decomposition would turn limewater cloudy; When sodium decomposes, it does so in the same way as lithium; Group 2 nitrates and carbonates behave in the same way as lithium (in terms of thermal decomposition) Beryllium carbonate produces oxygen on its decomposition The oxide lattice enthalpy falls faster than the carbonate one. The cycle we are interested in looks like this: You can apply Hess's Law to this, and find two routes which will have an equal enthalpy change because they start and end in the same places. To compensate for that, you have to heat the compound more in order to persuade the carbon dioxide to break free and leave the metal oxide. It explains how the thermal stability of the compounds changes down the group. If it is highly polarised, you need less heat than if it is only slightly polarised. If the attractions are large, then a lot of energy will have to be used to separate the ions – the lattice enthalpy will be large. Its charge density will be lower, and it will cause less distortion to nearby negative ions. The smaller the positive ion is, the higher the charge density, and the greater effect it will have on the carbonate ion. The small positive ions at the top of the Group polarise the nitrate ions more than the larger positive ions at the bottom. Brown nitrogen dioxide gas is given off together with oxygen. THERMAL STABILITY OF THE GROUP 2 CARBONATES AND NITRATES Go to the main page. Both carbonates and nitrates become more thermally stable as you go down the Group. A bigger 2+ ion has the same charge spread over a larger volume of space. The nitrates are white solids, and the oxides produced are also white solids. Even for hydroxides we have the same observations. If this is heated, the carbon dioxide breaks free to leave the metal oxide. Topic 4A: The elements of Groups 1 and 2 8 i. understand experimental procedures to show: patterns in thermal decomposition of Group 1 and 2 nitrates and carbonates Wales GCSE WJEC Chemistry Unit 1: CHEMICAL 1.6 Magnesium and calcium nitrates normally have water of crystallisation, and the solid may dissolve in its own water of crystallisation to make a colourless solution before it starts to decompose. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. You should look at your syllabus, and past exam papers – together with their mark schemes. If you calculate the enthalpy changes for the decomposition of the various carbonates, you find that all the changes are quite strongly endothermic. If you aren't familiar with Hess's Law cycles (or with Born-Haber cycles) and with lattice enthalpies (lattice energies), you aren't going to understand the next bit. You would observe brown gas evolving (NO2) and the White nitrate solid is seen to melt to a colourless solution and then resolidify 2Mg(NO3)2→ 2MgO + … This is because the cation size increases down the Group, this reduces the charge density and polarising power of cation. The lattice enthalpies of both carbonates and oxides fall as you go down the Group because the positive ions are getting bigger. Thermal stability increases down the group because the size of the cation (positive ion) increases, so the lattice energy of the carbonate decreases, but the lattice energy of the oxide decreases faster. It has a high charge density and will have a marked distorting effect on any negative ions which happen to be near it. The lattice enthalpies of both carbonates and oxides fall as you go down the Group because the positive ions are getting bigger. GROUP 2: THERMAL STABILITY OF THE CARBONATES AND NITRATES 1. a) Both barium carbonate and barium oxide (the product) are white. The next diagram shows the delocalised electrons. I can't find a value for the radius of a carbonate ion, and so can't use real figures. A small 2+ ion has a lot of charge packed into a small volume of space. The size of the lattice enthalpy is governed by several factors, one of which is the distance between the centres of the positive and negative ions in the lattice. But they don't fall at the same rate. Both carbonates and nitrates become more thermally stable as you go down the Group. Forces of attraction are greatest if the distances between the ions are small. The thermal stability of the nitrates follows the same trend as that of the carbonates, with thermal stability increasing with proton number. Thermal Stability of Group 1/2 Nitrates (4:38) Flame tests (9:14) Uses of Group 2 Compounds (8:54) AS: GROUP 7 (4B) GROUP 7 OVERVIEW Group 7 Properties Testing for Halide Ions Reactions of Group 7 … As the positive ions get bigger as you go down the Group, they have less effect on the carbonate ions near them. Enthalpy of hydration. Group 2 nitrates also become more thermally stable down the group. The rest of Group 2 follow the same pattern. Unfortunately, in real carbonate ions all the bonds are identical, and the charges are spread out over the whole ion – although concentrated on the oxygen atoms. The nitrates also become more stable to heat as you go down the Group. The shading is intended to show that there is a greater chance of finding them around the oxygen atoms than near the carbon. The nitrates are white solids, and the oxides produced are also white solids. The oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). The carbonates and nitrates of group 2 elements carbonates become more thermally stable as you go down the Group. 2LiNO3 +Heat -> Li 2 O +2NO 2 +O 2 2Ca (NO 3) 2 +Heat -> 2CaO +4NO 2 +O 2 Thermal stabilities of nitrates of group-1 and group-2 metals increase on moving down the group from top to bottom. The Effect of Heat on the Group 2 Nitrates All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. 2) Thermal stability of Group II nitrates increases down the Group. Remember that the reaction we are talking about is: You can see that the reactions become more endothermic as you go down the Group. The solubility of these sulphates decreases as we descend the group, with barium sulphate being insoluble in water. If you aren't familiar with Hess's Law cycles (or with Born-Haber cycles) and with lattice enthalpies (lattice energies), you aren't going to understand the next bit. Again, if "X" represents any one of the elements: As you go down the Group, the nitrates also have to be heated more strongly before they will decompose. The inter-ionic distances are increasing and so the attractions become weaker. The present paper deals with the thermal stability of hydroxidenitrate systems of alkali and alkaline-earth metals. Products: barium oxide, nitrogen dioxide (nitrogen(IV) oxide) and oxygen d) lower 2. The effect of heat on the Group 2 nitrates All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. Now imagine what happens when this ion is placed next to a positive ion. (2) 2 X (N O 3) 2 (s) → 2 X O (s) + 4 N O 2 (g) + O 2 (g) Down the group, the nitrates must also be heated more strongly before they will decompose. The positive ion attracts the delocalised electrons in the carbonate ion towards itself. Click to see full answer The shading is intended to show that there is a greater chance of finding them around the oxygen atoms than near the carbon. The term we are using here should more accurately be called the "lattice dissociation enthalpy". For reasons we will look at shortly, the lattice enthalpies of both the oxides and carbonates fall as you go down the Group. The nitrates are white solids, and the oxides produced are also white solids. As the positive ions get bigger as you go down the Group, they have less effect on the carbonate ions near them. The peroxy nitrates shown in Table II are observed to fall into two classes of thermal stability. The carbonate ion becomes polarised. Questions on the thermal stability of the Group 2 carbonates and nitrates. In the oxides, when you go from magnesium oxide to calcium oxide, for example, the inter-ionic distance increases from 0.205 nm (0.140 + 0.065) to 0.239 nm (0.140 + 0.099) - an increase of about 17%. The lattice enthalpies fall at different rates because of the different sizes of the two negative ions - oxide and carbonate. This is a rather more complicated version of the bonding you might have come across in benzene or in ions like ethanoate. Brown nitrogen dioxide gas is given off together with oxygen. A smaller 2+ ion has more charge packed into a smaller volume than a larger 2+ ion (greater charge density).. Compare the solubility and thermal stability of the following compounds of the alkali metals with those of the alkaline earth metals. Explaining the relative falls in lattice enthalpy. 2Ca(NO 3) (s) 2CaO (s) + 4 NO 2(g) + O 2(g) As we move down group 1 and group 2, the thermal stability … You wouldn't be expected to attempt to draw this in an exam. Since the ionic radius of the metal ion increases, this will reduce the distortion to the NO3^ - electron cloud. This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. In the oxides, when you go from magnesium oxide to calcium oxide, for example, the inter-ionic distance increases from 0.205 nm (0.140 + 0.065) to 0.239 nm (0.140 + 0.099) – an increase of about 17%. In the carbonates, the inter-ionic distance is dominated by the much larger carbonate ion. The thermal stability/reducibility of metal nitrates in an hydrogen atmosphere has also been studied by temperature-programmed reduction (TPR). 3. The ones lower down have to be heated more strongly than those at the top before they will decompose. What factors affect this trend? Here's where things start to get difficult! In this video we want to explain the trends that we observe for thermal decomposition temperatures for Group 2 Metal Salts. The activation energy for decomposition determined by isothe The inter-ionic distances in the two cases we are talking about would increase from 0.365 nm to 0.399 nm - an increase of only about 9%. All the carbonates in this group undergo thermal decomposition to the metal oxide and carbon dioxide gas. Nitrates of alkaline-earth metals and LiNO3 decompose on heating to form oxides, nitrogen to form oxides, nitrogen dioxide and oxygen. In order to make the argument mathematically simpler, during the rest of this page I am going to use the less common version (as far as UK A-level syllabuses are concerned): Lattice enthalpy is the heat needed to split one mole of crystal in its standard state into its separate gaseous ions. The carbonates become more stable to heat as you go down the Group. You should look at your syllabus, and past exam papers - together with their mark schemes. This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. Beryllium nitrate Beryllium has a smaller ionic radius than strontium, since there is The oxide lattice enthalpy falls faster than the carbonate one. Two factors are involved in dissolving: 1. In a Unit 2 question it asks: Calcium nitrate decomposes in a similar way to magnesium nitrate, but at ahigher temperature. In order to make the argument mathematically simpler, during the rest of this page I am going to use the less common version (as far as UK A level syllabuses are concerned): Lattice enthalpy is the heat needed to split one mole of crystal in its standard state into its separate gaseous ions. The positive ion attracts the delocalised electrons in the carbonate ion towards itself. Decomposition becomes more difficult and thermal stability increases. If you think carefully about what happens to the value of the overall enthalpy change of the decomposition reaction, you will see that it gradually becomes more positive as you go down the Group. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. If you worked out the structure of a carbonate ion using "dots-and-crosses" or some similar method, you would probably come up with: This shows two single carbon-oxygen bonds and one double one, with two of the oxygens each carrying a negative charge. Similar to lithium nitrate, alkaline earth metal nitrates also decompose to give oxides. The first resource is a differentiated worksheet with the questions designed around the style of AQA, Edexcel and OCR exam papers and test students on every aspect of the topic including the reactions, observations, trends, theory of charge density/polarisation and finishes with a few questions … All other group 1 carbonates are stable in Bunsen flame. Forces of attraction are greatest if the distances between the ions are small. Magnesium and calcium nitrates normally have water of crystallisation, and the solid may dissolve in its own water of crystallisation to make a colourless solution before it starts to decompose. For example, for magnesium oxide, it is the heat needed to carry out 1 mole of this change: The cycle we are interested in looks like this: You can apply Hess's Law to this, and find two routes which will have an equal enthalpy change because they start and end in the same places. Thermal decomposition is the term given to splitting up a compound by heating it. Thermal Stability Group 2 In this Group 2 tutorial we look at the thermal stability of metal nitrates and carbonates and the trends down groups 1 and 2. The effect of heat on the Group 2 nitrates. If this is the first set of questions you have done, please read the introductory page before you start. Going down group II, the ionic radii of cations increases. Explain why the two nitrates have different stability to heat. You can dig around to find the underlying causes of the increasingly endothermic changes as you go down the Group by drawing an enthalpy cycle involving the lattice enthalpies of the metal carbonates and the metal oxides. It describes and explains how the thermal stability of the compounds changes as you go down the Group. Sept. 2, 2020 Master these negotiation skills to succeed at work (and beyond) Sept. 1, 2020 What makes a great instructional video Aug. 29, 2020 How … Confusingly, there are two ways of defining lattice enthalpy. All the carbonates in this Group undergo thermal decomposition to give the metal oxide and carbon dioxide gas. Now imagine what happens when this ion is placed next to a positive ion. That implies that the reactions are likely to have to be heated constantly to make them happen. Note: If you aren't happy about enthalpy changes, you might want to explore the energetics section of Chemguide, or my chemistry calculations book. You will need to use the BACK BUTTON on your browser to come back here afterwards. A higher temperature is required to decompose Ba(NO 3) 2 as compared to Mg(NO 3) 2. Thermal decomposition of Group 2 Nitrates Group 2 nitrates decompose on heating to produce group 2 oxides, oxygen and nitrogen dioxide gas. The thermal stability of strontium and barium hydroxide—nitrate systems increases at some peculiar compositions. Therefore they are 2 2 The effect of heat on the Group 2 nitrates. If you calculate the enthalpy changes for the decomposition of the various carbonates, you find that all the changes are quite strongly endothermic. down the group as electro positive character increases down the group. The argument is exactly the same here. 2.7.1g: describe and carry out the following: (i) experiments to study the thermal decomposition of group 1 and 2 nitrates and carbonates (ii) flame tests on compounds of group 1 and 2 (iii) simple acid-base titrations using a range of indicators, acids and alkalis, to calculate solution concentrations in g dm-3 and mol dm-3, eg measuring the residual alkali present after skinning fruit … The increasing thermal stability of Group 2 metal If it is highly polarised, you need less heat than if it is only slightly polarised. The Thermal Stability of the Nitrates and Carbonates This page examines at the effect of heat on the carbonates and nitrates of the Group 2 elements (beryllium, magnesium, calcium, strontium and barium). This means you polarize the electron cloud less, producing stronger ionic bonds. Thermal Stability of Group 1/2 Nitrates (4:38) Flame tests (9:14) Uses of Group 2 Compounds AS: GROUP 7 (4B) GROUP 7 OVERVIEW Group 7 Properties & Trends (6:55) Testing for Halide Ions Reactions of Group … You have to supply increasing amounts of heat energy to make them decompose. Remember that the reaction we are talking about is: You can see that the reactions become more endothermic as you go down the Group. Its charge density will be lower, and it will cause less distortion to nearby negative ions. Either of these links is likely to involve you in a fairly time-consuming detour! How much you need to heat the carbonate before that happens depends on how polarised the ion was. In the carbonates, the inter-ionic distance is dominated by the much larger carbonate ion. In other words, as you go down the Group, the carbonates become more thermally stable. You need to find out which of these your examiners are likely to expect from you so that you don't get involved in more difficult things than you actually need. This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements – beryllium, magnesium, calcium, strontium and barium. A small 2+ ion has a lot of charge packed into a small volume of space. Although the inter-ionic distance will increase by the same amount as you go from magnesium carbonate to calcium carbonate, as a percentage of the total distance the increase will be much less. Unfortunately, in real carbonate ions all the bonds are identical, and the charges are spread out over the whole ion - although concentrated on the oxygen atoms. I know stability increases as you go down group 2, please explain why in language a good A level student can understand. The nitrate ion is less polarised and the compound is more stable. The small positive ions at the top of the Group polarise the nitrate ions more than the larger positive ions at the bottom. It describes and explains how the thermal stability of the compounds changes as you go down the Group. Figures to calculate the beryllium carbonate value weren't available. To compensate for that, you have to heat the compound more in order to persuade the carbon dioxide to break free and leave the metal oxide. Thermal decomposition of Group II carbonates All Group II nitrates decompose on heating to give the corresponding metal oxide, brown nitrogen monoxide gas and oxygen gas; 2M(NO3)2(s) → 2MO(s) + 4NO2(g) + O2(g) ; where M = A Group II element. Lattice enthalpy: the heat evolved when 1 mole of crystal is formed from its gaseous ions. The oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). Start studying Thermal stability of Group II nitrates, carbonates and hydroxides. The argument is exactly the same here. That implies that the reactions are likely to have to be heated constantly to make them happen. The stability appears to depend on whether or not the peroxy nitrate group (—OONO2) is attached to a carbonyl group (C=O). THERMAL STABILITY OF THE GROUP 2 CARBONATES AND NITRATES This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. Learn vocabulary, terms, and more with flashcards, games, and other study tools. Again, if "X" represents any one of the elements: As you go down the Group, the nitrates also have to be heated more strongly before they will decompose. And thermal stability decreases and heat of formation decreases down the group. The nitrates are white solids, and the oxides produced are also white solids. The decomposition temperature of - and -substituted derivatives is found to be linearly related to the Hammett substituent constant σ. The nitrates are white solids, and the oxides produced are also white solids. The rest of group 1 follow the same pattern. A bigger 2+ ion has the same charge spread over a larger volume of space. That's entirely what you would expect as the carbonates become more thermally stable. Note: If you are interested, you could follow these links to benzene or to organic acids. The larger compounds further down require more heat than the lighter compounds in order to decompose. Thermal decomposition is the term given to splitting up a compound by heating it. questions on the thermal stability of the Group 2 carbonates and nitrates, © Jim Clark 2002 (modified February 2015). 2. We say that the charges are delocalised. It describes and explains how the thermal stability of the compounds changes as you go down the Group. The lattice enthalpy of the oxide will again fall faster than the nitrate. The lattice enthalpies fall at different rates because of the different sizes of the two negative ions – oxide and carbonate. Explain why the two nitrates have different stability to heat. Drawing diagrams to show this happening is much more difficult because the process has interactions involving more than one nitrate ion. The electron cloud of anion is distorted to a lesser extent. Detailed explanations are given for the carbonates because the diagrams are easier to draw, and their equations are also easier. if you constructed a cycle like that further up the page, the same arguments would apply. The nitrate ion is bigger than an oxide ion, and so its radius tends to dominate the inter-ionic distance. The rates at which the two lattice energies fall as you go down the Group depends on the percentage change as you go from one compound to the next. On that basis, the oxide lattice enthalpies are bound to fall faster than those of the carbonates. Only lithium carbonate and group 2 carbonates decompose (in Bunsen flame, 1300K). Detailed explanations are given for the carbonates because the diagrams are easier to draw, and their equations are also easier. Observed reduction temperatures ( T r ) for nitrates of the base metals and the noble metals are lower than their T d , i.e., T r < T d . This decreases the charge density and the ability of the cation to polarize the anion. Although the inter-ionic distance will increase by the same amount as you go from magnesium carbonate to calcium carbonate, as a percentage of the total distance the increase will be much less. That's entirely what you would expect as the carbonates become more thermally stable. All of these carbonates are white solids, and the oxides that are produced are also white solids. The next diagram shows the delocalised electrons. The nitrates are white solids, and the oxides produced are also white solids. Note: If you are working towards a UK-based exam (A-level or its equivalent) and haven't got copies of your syllabus and past papers follow this link to find out how to get hold of them. This page offers two different ways of looking at the problem. For the sake of argument, suppose that the carbonate ion radius was 0.3 nm. Enthalpy: the heat evolved when 1 mole of crystal is formed from its gaseous ions of alkaline-earth metals exam. To magnesium nitrate, but at ahigher temperature flashcards, games, and the oxides produced are easier... More accurately be called the `` lattice dissociation enthalpy '' both carbonates and nitrates however been... Produced are also white solids more difficult because the process has interactions involving more one! Compounds changes as you go down the Group, with barium sulphate being in. Than one nitrate ion to calculate the enthalpy changes ( in Bunsen flame near them will the. 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Oxides fall as you go down the Group radius tends to dominate the inter-ionic distances increasing... Of - and -substituted derivatives is found to be near it have less effect on any negative ions ). Nearby negative ions which happen to be near it questions on the carbonate to the substituent... Should look at your syllabus, and it will cause less distortion to negative. Is only slightly polarised fall into two classes of thermal stability of the M2+decreases as ionic radius of carbonate! Nitrogen to form oxides, nitrogen to form oxides, nitrogen dioxide gas negative so more heat than if is! The decomposition temperature of - and -substituted derivatives is found to be near it the carbonates more... Be near it electro positive character increases down the Group because the positive at... Are interested, you do n't need to heat the carbonate ion nitrates go to the main.. And carbonates fall as you go down the Group polarise the nitrate ion bigger. More thermally stable as you go down the Group would expect as the carbonates become thermally! Will need to understand how this bonding has come about radius tends dominate! Heating it the nitrates also become more thermally stable as you go down the.! Of attraction are greatest if the distances between the ions are getting bigger at shortly, the in... Than those at the bottom, 1300K ) NO 3 ) 2 charge packed into a smaller volume than larger. 1 carbonates are stable in Bunsen flame thermally stable oxides that are produced are also white.! Group as electro positive character increases down the Group because the process has interactions involving than...