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. 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. 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. Compare the solubility and thermal stability of the following compounds of the alkali metals with those of the alkaline earth metals. 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} The rest of group 1 follow the same pattern. \text{Mg}O_{s} \longrightarrow \text{Mg}^{2+}_{(g)} + O^{2-}_{(g)} \\{\Delta}H_{\text{lattice}} = +3889~kJ~mol^{-1} If it is highly polarised, you need less heat than if it is only slightly polarised. Explaining the trend in terms of the polarising ability of the positive ion. The shading is intended to show that there is a greater chance of finding them around the oxygen atoms than near the carbon. The electron cloud of anion is distorted to a lesser extent. It describes and explains how the thermal stability of the compounds changes as you go down the Group. 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. That's entirely what you would expect as the carbonates become more thermally stable. You wouldn't be expected to attempt to draw this in an exam. The effect of heat on the Group 2 nitrates. Even for hydroxides we have the same observations. b) lower c) A white solid producing a … 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. We say that the charges are delocalised. Confusingly, there are two ways of defining lattice enthalpy. 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. Confusingly, there are two ways of defining lattice enthalpy. Thermal decomposition of Group 2 Nitrates Group 2 nitrates decompose on heating to produce group 2 oxides, oxygen and nitrogen dioxide gas. As the positive ions get bigger as you go down the Group, they have less effect on the carbonate ions near them. Drawing diagrams to show this happening is much more difficult because the process has interactions involving more than one nitrate ion. Here's where things start to get difficult! questions on the thermal stability of the Group 2 carbonates and nitrates, © Jim Clark 2002 (modified February 2015). The next diagram shows the delocalised electrons. The thermal stability of the nitrates follows the same trend as that of the carbonates, with thermal stability increasing with proton number. Group 2 nitrates become more thermally stable down the group. The increasing thermal stability of Group 2 metal Click to see full answer A higher temperature is required to decompose Ba(NO 3) 2 as compared to Mg(NO 3) 2. You wouldn't be expected to attempt to draw this in an exam. The nitrates are white solids, and the oxides produced are also white solids. And thermal stability decreases and heat of formation decreases down the group. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. The nitrates are white solids, and the oxides produced are also white solids. Detailed explanations are given for the carbonates because the diagrams are easier to draw, and their equations are also easier. The carbonates become more stable to heat as you go down the Group. In other words, as you go down the Group, the carbonates become more thermally stable. In the carbonates, the inter-ionic distance is dominated by the much larger carbonate ion. The smaller the positive ion is, the higher the charge density, and the greater effect it will have on the carbonate ion. 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. Its charge density will be lower, and it will cause less distortion to nearby negative ions. 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. The activation energy for decomposition determined by isothe The smaller the positive ion is, the higher the charge density, and the greater effect it will have on the carbonate ion. Both carbonates and nitrates of Group 2 elements become more thermally stable down the group. The enthalpy changes (in kJ mol-1) which I calculated from enthalpy changes of formation are given in the table. Its charge density will be lower, and it will cause less distortion to nearby negative ions. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. Group 2 nitrates also become more thermally stable down the group. 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. Don't waste your time looking at it. Exactly the same arguments apply to the nitrates. 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 … It explains how the thermal stability of the compounds changes down the group. 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 carbonates become more stable to heat as you go down the Group. The oxide lattice enthalpy falls faster than the carbonate one. down the group as electro positive character increases down the group. That implies that the reactions are likely to have to be heated constantly to make them happen. We say that the charges are delocalised. 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%. Now imagine what happens when this ion is placed next to a positive ion. The nitrates are white solids, and the oxides produced are also white solids. All the carbonates in this group undergo thermal decomposition to the metal oxide and carbon dioxide gas. The lattice enthalpy of the oxide will again fall faster than the nitrate. The term we are using here should more accurately be called the "lattice dissociation enthalpy". This is because the cation size increases down the Group, this reduces the charge density and polarising power of cation. 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 energy 2. The thermal stability/reducibility of metal nitrates in an hydrogen atmosphere has also been studied by temperature-programmed reduction (TPR). Learn vocabulary, terms, and more with flashcards, games, and other study tools. The ones lower down have to be heated more strongly than those at the top before they will decompose. You should look at your syllabus, and past exam papers - together with their mark schemes. But they don't fall at the same rate. Brown nitrogen dioxide gas is given off together with oxygen. Explaining the trend in terms of the energetics of the process. How much you need to heat the carbonate before that happens depends on how polarised the ion was. Exactly the same arguments apply to the nitrates. Thermal decomposition of Group II carbonates 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. That implies that the reactions are likely to have to be heated constantly to make them happen. 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. Note: If you are interested, you could follow these links to benzene or to organic acids. 3. 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. Either of these links is likely to involve you in a fairly time-consuming detour! Going down group II, the ionic radii of cations increases. If this is heated, the carbon dioxide breaks free to leave the metal oxide. 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. For the sake of argument, suppose that the carbonate ion radius was 0.3 nm. Remember that the reaction we are talking about is: You can see that the reactions become more endothermic as you go down the Group. On that basis, the oxide lattice enthalpies are bound to fall faster than those of the carbonates. The lattice enthalpies of both carbonates and oxides fall as you go down the Group because the positive ions are getting bigger. 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. 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. 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. If it is highly polarised, you need less heat than if it is only slightly polarised. This means that the enthalpy change from the carbonate to the oxide becomes more negative so more heat is needed to decompose it. Similar to lithium nitrate, alkaline earth metal nitrates also decompose to give oxides. Here's where things start to get difficult! You will need to use the BACK BUTTON on your browser to come back here afterwards. Brown nitrogen dioxide gas is given off together with oxygen. Hydrides liberate hydrogen at anode on electrolysis. 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 oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). The solubility of these sulphates decreases as we descend the group, with barium sulphate being insoluble in water. The shading is intended to show that there is a greater chance of finding them around the oxygen atoms than near the carbon. 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 … The carbonate ion becomes polarised. b) lower c) A white solid producing a brown gas and leaving a white solid. The oxide lattice enthalpy falls faster than the carbonate one. (substitute Na, K etc where Li is). The carbonate ion becomes polarised. A small 2+ ion has a lot of charge packed into a small volume of space. The 2 I know stability increases as you go down group 2, please explain why in language a good A level student can understand. It has been The nitrate ion is bigger than an oxide ion, and so its radius tends to dominate the inter-ionic distance. The thermal stability of ring-substituted arylammonium nitrates has been investigated using thermal methods of analysis. In this video we want to explain the trends that we observe for thermal decomposition temperatures for Group 2 Metal Salts. The decomposition temperature of - and -substituted derivatives is found to be linearly related to the Hammett substituent constant σ. I can't find a value for the radius of a carbonate ion, and so can't use real figures. 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. For reasons we will look at shortly, the lattice enthalpies of both the oxides and carbonates fall as you go down the Group. If you calculate the enthalpy changes for the decomposition of the various carbonates, you find that all the changes are quite strongly endothermic. GROUP 2: THERMAL STABILITY OF THE CARBONATES AND NITRATES 1. a) Both barium carbonate and barium oxide (the product) are white. Both carbonates and nitrates become more thermally stable as you go down the Group. The inter-ionic distances are increasing and so the attractions become weaker. This page offers two different ways of looking at the problem. 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%. 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%. 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 thermal stability of strontium and barium hydroxide—nitrate systems increases at some peculiar compositions. The ones lower down have to be heated more strongly than those at the top before they will decompose. Thermal decomposition is the term given to splitting up a compound by heating it. Forces of attraction are greatest if the distances between the ions are small. It describes and explains how the thermal stability of the compounds changes as you go down the Group. 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. All of these carbonates are white solids, and the oxides that are produced are also white solids. The nitrates also become more stable to heat as you go down the Group. 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. Nitrates of alkaline-earth metals and LiNO3 decompose on heating to form oxides, nitrogen to form oxides, nitrogen dioxide and oxygen. 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. If this is the first set of questions you have done, please read the introductory page before you start. A small 2+ ion has a lot of charge packed into a small volume of space. 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. 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. 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 This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. 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. A bigger 2+ ion has the same charge spread over a larger volume of space. The inter-ionic distances are increasing and so the attractions become weaker. 2) Thermal stability of Group II nitrates increases down the Group. Only lithium carbonate and group 2 carbonates decompose (in Bunsen flame, 1300K). The carbonates and nitrates of group 2 elements carbonates become more thermally stable as you go down the Group. The oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). Brown nitrogen dioxide gas is given off together with oxygen. The carbonates and nitrates of group 2 elements carbonates become more thermally stable as you go down the Group. 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. Detailed explanations are given for the carbonates because the diagrams are easier to draw, and their equations are also easier. 1. 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. This is a rather more complicated version of the bonding you might have come across in benzene or in ions like ethanoate. 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 … This page offers two different ways of looking at the problem. The effect of heat on the Group 2 carbonates. Decomposition becomes more difficult and thermal stability increases. If this is heated, the carbon dioxide breaks free to leave the metal oxide. Also, does thermal stability increase or decrease as you go down group … On that basis, the oxide lattice enthalpies are bound to fall faster than those of the carbonates. The lattice enthalpy of the oxide will again fall faster than the nitrate. What factors affect this trend? All of these carbonates are white solids, and the oxides that are produced are also white solids. 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. Brown nitrogen dioxide gas is given off together with oxygen. Which of these statements is correct? 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 … Explain why the two nitrates have different stability to heat. Brown nitrogen dioxide gas is given off together with oxygen. 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. Your browser to come BACK here afterwards size increases down the Group polarise the nitrate ions more than the ion... 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