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 oxide lattice enthalpy falls faster than the carbonate one. 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. Both carbonates and nitrates become more thermally stable as you go down the Group. Here's where things start to get difficult! The positive ion attracts the delocalised electrons in the carbonate ion towards itself. What factors affect this trend? If you calculate the enthalpy changes for the decomposition of the various carbonates, you find that all the changes are quite strongly endothermic. Explaining the trend in terms of the energetics of the process. Forces of attraction are greatest if the distances between the ions are small. 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 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. 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. A small 2+ ion has a lot of charge packed into a small volume of space. Now imagine what happens when this ion is placed next to a positive ion. We say that the charges are delocalised. 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. 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%. The ones lower down have to be heated more strongly than those at the top before they will decompose. A bigger 2+ ion has the same charge spread over a larger volume of space. The lattice enthalpies fall at different rates because of the different sizes of the two negative ions â oxide and carbonate. The activation energy for decomposition determined by isothe Beryllium nitrate Beryllium has a smaller ionic radius than strontium, since there is 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. For reasons we will look at shortly, the lattice enthalpies of both the oxides and carbonates fall as you go down the Group. If it is highly polarised, you need less heat than if it is only slightly polarised. 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. 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. That's entirely what you would expect as the carbonates become more thermally stable. This page offers two different ways of looking at the problem. The present paper deals with the thermal stability of hydroxidenitrate systems of alkali and alkaline-earth metals. You wouldn't be expected to attempt to draw this in an exam. The oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). questions on the thermal stability of the Group 2 carbonates and nitrates, © Jim Clark 2002 (modified February 2015). That implies that the reactions are likely to have to be heated constantly to make them happen. 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. The carbonate ion becomes polarised. This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. The effect of heat on the Group 2 nitrates. The thermal stability/reducibility of metal nitrates in an hydrogen atmosphere has also been studied by temperature-programmed reduction (TPR). All the carbonates in this group undergo thermal decomposition to the metal oxide and carbon dioxide gas. The thermal stability of ring-substituted arylammonium nitrates has been investigated using thermal methods of analysis. Its charge density will be lower, and it will cause less distortion to nearby negative ions. All the carbonates in this Group undergo thermal decomposition to give the metal oxide and carbon dioxide gas. If this is heated, the carbon dioxide breaks free to leave the metal oxide. \end{gathered}. The nitrates are white solids, and the oxides produced are also white solids. 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. 1. The next diagram shows the delocalised electrons. 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. 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 the sake of argument, suppose that the carbonate ion radius was 0.3 nm. The carbonates become more stable to heat as you go down the Group. Thermal decomposition is the term given to splitting up a compound by heating it. Explain why the two nitrates have different stability to heat. Unfortunately, in real carbonate ions all the bonds are identical, and the charges are spread out over the whole ion â although concentrated on the oxygen atoms. Forces of attraction are greatest if the distances between the ions are small. It has been Don't waste your time looking at it. In the carbonates, the inter-ionic distance is dominated by the much larger carbonate ion. 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 … But they don't fall at the same rate. I can't find a value for the radius of a carbonate ion, and so can't use real figures. Detailed explanations are given for the carbonates because the diagrams are easier to draw, and their equations are also easier. Thermal decomposition of Group II carbonates This is because the cation size increases down the Group, this reduces the charge density and polarising power of cation. 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. The ones lower down have to be heated more strongly than those at the top before they will decompose. The nitrates also become more stable to heat as you go down the Group. The increasing thermal stability of Group 2 metal The nitrate ion is bigger than an oxide ion, and so its radius tends to dominate the inter-ionic distance. 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. 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. Its charge density will be lower, and it will cause less distortion to nearby negative ions. The lattice enthalpy of the oxide will again fall faster than the nitrate. In group 1 and 2, the nitrates and carbonates get more stable down the group. I know stability increases as you go down group 2, please explain why in language a good A level student can understand. The inter-ionic distances are increasing and so the attractions become weaker. For the purposes of this topic, you don't need to understand how this bonding has come about. if you constructed a cycle like that further up the page, the same arguments would apply. For the purposes of this topic, you don't need to understand how this bonding has come about. The nitrate ion is bigger than an oxide ion, and so its radius tends to dominate the inter-ionic distance. It describes and explains how the thermal stability of the compounds changes as you go down the Group. 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. 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. You have to supply increasing amounts of heat energy to make them decompose. You have to supply increasing amounts of heat energy to make them decompose. 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. You wouldn't be expected to attempt to draw this in an exam. On that basis, the oxide lattice enthalpies are bound to fall faster than those of the carbonates. Confusingly, there are two ways of defining lattice enthalpy. As the positive ions get bigger as you go down the Group, they have less effect on the carbonate ions near them. Brown nitrogen dioxide gas is given off together with oxygen. That's entirely what you would expect as the carbonates become more thermally stable. Explain why the two nitrates have different stability to heat. A bigger 2+ ion has the same charge spread over a larger volume of space. (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. 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. 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. Hydrides liberate hydrogen at anode on electrolysis. 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. 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. 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 … Note: If you aren't happy about enthalpy changes, you might want to explore the energetics section of Chemguide, or my chemistry calculations book. The thermal stability of hydroxide-nitrate systems has, however, been discussed in few papers. Questions on the thermal stability of the Group 2 carbonates and nitrates. The argument is exactly the same here. Explaining the trend in terms of the polarising ability of the positive ion. The reason, once more, is that the polarising power of the M2+decreases as ionic radius increases. 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. Eight resources on the thermal decomposition of the group 1 and 2 nitrates and carbonates. Thermal decomposition of Group 2 Nitrates Group 2 nitrates decompose on heating to produce group 2 oxides, oxygen and nitrogen dioxide gas. 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. The shading is intended to show that there is a greater chance of finding them around the oxygen atoms than near the carbon. 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. Here's where things start to get difficult! Both carbonates and nitrates become more thermally stable as you go down the Group. The ones lower down have to be heated more strongly than those at the top before they will decompose. Decomposition becomes more difficult and thermal stability increases. b) lower c) A white solid producing a brown gas and leaving a white solid. In a Unit 2 question it asks: Calcium nitrate decomposes in a similar way to magnesium nitrate, but at ahigher temperature. And thermal stability decreases and heat of formation decreases down the group. 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. Compare the solubility and thermal stability of the following compounds of the alkali metals with those of the alkaline earth metals. The small positive ions at the top of the Group polarise the nitrate ions more than the larger positive ions at the bottom. Since both 2-methyl-2-butanol nitrate and 2-methyl-2-propanol nitrate exhibited low thermal stability, they were not distilled from the reaction solvent diethyl ether. Which of these statements is correct? If this is heated, the carbon dioxide breaks free to leave the metal oxide. The lattice enthalpies of both carbonates and oxides fall as you go down the Group because the positive ions are getting bigger. Similar to lithium nitrate, alkaline earth metal nitrates also decompose to give oxides. 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. Start studying Thermal stability of Group II nitrates, carbonates and hydroxides. The effect of heat on the Group 2 nitrates. On that basis, the oxide lattice enthalpies are bound to fall faster than those of the carbonates. The nitrates are white solids, and the oxides produced are also white solids. In other words, as you go down the Group, the carbonates become more thermally stable. It describes and explains how the thermal stability of the compounds changes as you go down the Group. 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. Lattice enthalpy: the heat evolved when 1 mole of crystal is formed from its gaseous ions. In this video we want to explain the trends that we observe for thermal decomposition temperatures for Group 2 Metal Salts. Figures to calculate the beryllium carbonate value weren't available. 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 . Brown nitrogen dioxide gas is given off together with oxygen. 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. 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 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. If it is highly polarised, you need less heat than if it is only slightly polarised. This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. The oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). 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. This means that the enthalpy change from the carbonate to the oxide becomes more negative so more heat is needed to decompose it. Exactly the same arguments apply to the nitrates. THERMAL STABILITY OF THE GROUP 2 CARBONATES AND NITRATES. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. 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 … The nitrates also become more stable to heat as you go down the Group. 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