A bigger 2+ ion has the same charge spread over a larger volume of space. 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 inter-ionic distances are increasing and so the attractions become weaker. Detailed explanations are given for the carbonates because the diagrams are easier to draw, and their equations are also easier. As the positive ions get bigger as you go down the Group, they have less effect on the carbonate ions near them. You should look at your syllabus, and past exam papers - together with their mark schemes. It describes and explains how the thermal stability of the compounds changes as you go down the Group. 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. Here's where things start to get difficult! The activation energy for decomposition determined by isothe Thermal decomposition is the term given to splitting up a compound by heating it. A smaller 2+ ion has more charge packed into a smaller volume than a larger 2+ ion (greater charge density).. The lattice enthalpies fall at different rates because of the different sizes of the two negative ions – oxide and carbonate. A small 2+ ion has a lot of charge packed into a small volume of space. 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 … The positive ion attracts the delocalised electrons in the carbonate ion towards itself. 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. Here's where things start to get difficult! The carbonates become more stable to heat as you go down the Group. For the sake of argument, suppose that the carbonate ion radius was 0.3 nm. I can't find a value for the radius of a carbonate ion, and so can't use real figures. It describes and explains how the thermal stability of the compounds changes as you go down the Group. Brown nitrogen dioxide gas is given off together with oxygen. If it is highly polarised, you need less heat than if it is only slightly polarised. The lattice enthalpy of the oxide will again fall faster than the nitrate. Drawing diagrams to show this happening is much more difficult because the process has interactions involving more than one nitrate ion. This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. It has a high charge density and will have a marked distorting effect on any negative ions which happen to be near it. 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. The lattice enthalpies of both carbonates and oxides fall as you go down the Group because the positive ions are getting bigger. Enthalpy of hydration. 2. You have to supply increasing amounts of heat energy to make them decompose. if you constructed a cycle like that further up the page, the same arguments would apply. Thermal decomposition of Group II carbonates The effect of heat on the Group 2 nitrates. Confusingly, there are two ways of defining lattice enthalpy. This page looks at the effect of heat on the carbonates and nitrates of the Group 2 elements - beryllium, magnesium, calcium, strontium and barium. 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. 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. Due to the large size of the sulphate anion there is little difference betw… In other words, as you go down the Group, the carbonates become more thermally stable. Brown nitrogen dioxide gas is given off together with oxygen. It describes and explains how the thermal stability of the compounds changes as you go down the Group. Similar to lithium nitrate, alkaline earth metal nitrates also decompose to give oxides. If this is the first set of questions you have done, please read the introductory page before you start. The thermal stability of the nitrates follows the same trend as that of the carbonates, with thermal stability increasing with proton number. But they don't fall at the same rate. For nitrates we notice the same trend. The electron cloud of anion is distorted to a lesser extent. Don't waste your time looking at it. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. Since the ionic radius of the metal ion increases, this will reduce the distortion to the NO3^ - electron cloud. Click to see full answer This page offers two different ways of looking at the problem. Which of these statements is correct? The next diagram shows the delocalised electrons. Both carbonates and nitrates become more thermally stable as you go down the Group. In group 1 and 2, the nitrates and carbonates get more stable down the group. Therefore they are 2 2 It describes and explains how the thermal stability of the compounds changes as you go down the Group. 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 nitrates also become more stable to heat as you go down the Group. The nitrates are white solids, and the oxides produced are also white solids. That implies that the reactions are likely to have to be heated constantly to make them happen. All the nitrates in this Group undergo thermal decomposition to give the metal oxide, nitrogen dioxide and oxygen. The calculated enthalpy changes (in kJ mol-1) are given in the table. Don't waste your time looking at it. 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 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). 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. Compare the solubility and thermal stability of the following compounds of the alkali metals with those of the alkaline earth metals. Brown nitrogen dioxide gas is given off together with oxygen. The effect of heat on the Group 2 nitrates. 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. The effect of heat on the Group 2 nitrates. 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 lattice enthalpies of both carbonates and oxides fall as you go down the Group because the positive ions are getting bigger. Only lithium carbonate and group 2 carbonates decompose (in Bunsen flame, 1300K). Beryllium nitrate Beryllium has a smaller ionic radius than strontium, since there is questions on the thermal stability of the Group 2 carbonates and nitrates, © Jim Clark 2002 (modified February 2015). On that basis, the oxide lattice enthalpies are bound to fall faster than those of the carbonates. For reasons we will look at shortly, the lattice enthalpies of both the oxides and carbonates fall as you go down the Group. 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. 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. down the group as electro positive character increases down the group. You wouldn't be expected to attempt to draw this in an exam. 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. All other group 1 carbonates are stable in Bunsen flame. Detailed explanations are given for the carbonates because the diagrams are easier to draw, and their equations are also easier. The nitrates also become more stable to heat as you go down the Group. 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%. You will need to use the BACK BUTTON on your browser to come back here afterwards. The ones lower down have to be heated more strongly than those at the top before they will decompose. I can't find a value for the radius of a carbonate ion, and so can't use real figures. If you calculate the enthalpy changes for the decomposition of the various carbonates, you find that all the changes are quite strongly endothermic. We say that the charges are delocalised. 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 . The rest of Group 2 follow the same pattern. 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. 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. 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 + … The nitrates are white solids, and the oxides produced are also white solids. 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 smaller the positive ion is, the higher the charge density, and the greater effect it will have on the carbonate ion. The lattice enthalpies fall at different rates because of the different sizes of the two negative ions - oxide and carbonate. The nitrate ion is bigger than an oxide ion, and so its radius tends to dominate the inter-ionic distance. You should look at your syllabus, and past exam papers – together with their mark schemes. 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 The 2 (substitute Na, K etc where Li is). 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 carbonates become more stable to heat as you go down the Group. The thermal stability of hydroxide-nitrate systems has, however, been discussed in few papers. Lattice enthalpy: the heat evolved when 1 mole of crystal is formed from its gaseous ions. GROUP 2: THERMAL STABILITY OF THE CARBONATES AND NITRATES 1. a) Both barium carbonate and barium oxide (the product) are white. (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. Learn vocabulary, terms, and more with flashcards, games, and other study tools. 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. 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 … 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. \end{gathered}. Start studying Thermal stability of Group II nitrates, carbonates and hydroxides. Eight resources on the thermal decomposition of the group 1 and 2 nitrates and carbonates. Exactly the same arguments apply to the nitrates. How much you need to heat the carbonate before that happens depends on how polarised the ion was. It explains how the thermal stability of the compounds changes down the group. It has been Products: barium oxide, nitrogen dioxide (nitrogen(IV) oxide) and oxygen d) lower 2. Now imagine what happens when this ion is placed next to a positive ion. Its charge density will be lower, and it will cause less distortion to nearby negative ions. THERMAL STABILITY OF THE GROUP 2 CARBONATES AND NITRATES Go to the main page. The reason, once more, is that the polarising power of the M2+decreases as ionic radius increases. Going down group II, the ionic radii of cations increases. 1. The increasing thermal stability of Group 2 metal 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%. Both carbonates and nitrates become more thermally stable as you go down the Group. 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. 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 larger compounds further down require more heat than the lighter compounds in order to decompose. 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. 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 This page offers two different ways of looking at the problem. The carbonate ion becomes polarised. The carbonates and nitrates of group 2 elements carbonates become more thermally stable as you go 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. 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. For the sake of argument, suppose that the carbonate ion radius was 0.3 nm. That's entirely what you would expect as the carbonates become more thermally stable. In other words, as you go down the Group, the carbonates become more thermally stable. All of these carbonates are white solids, and the oxides that are produced are also white solids. 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. Thermal decomposition is the term given to splitting up a compound by heating it. All of these carbonates are white solids, and the oxides that are produced are also white solids. 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. Figures to calculate the beryllium carbonate value weren't available. 1. 2. The carbonates and nitrates of group 2 elements carbonates become more thermally stable as you go down the Group. Now imagine what happens when this ion is placed next to a positive ion. The oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). You have to supply increasing amounts of heat energy to make them decompose. Explaining the trend in terms of the energetics of the process. The nitrates are white solids, and the oxides produced are also white solids. This is because the cation size increases down the Group, this reduces the charge density and polarising power of cation. The ones lower down have to be heated more strongly than those at the top 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. The present paper deals with the thermal stability of hydroxidenitrate systems of alkali and alkaline-earth metals. Even for hydroxides we have the same observations. Questions on the thermal stability of the Group 2 carbonates and nitrates. 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 oxide ion is relatively small for a negative ion (0.140 nm), whereas the carbonate ion is large (no figure available). Lattice energy 2. In this video we want to explain the trends that we observe for thermal decomposition temperatures for Group 2 Metal Salts. Drawing diagrams to show this happening is much more difficult because the process has interactions involving more than one nitrate ion. 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. Note: If you are interested, you could follow these links to benzene or to organic acids. 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. Also, does thermal stability increase or decrease as you go down group … You wouldn't be expected to attempt to draw this in an exam. 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 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. b) lower c) A white solid producing a … We say that the charges are delocalised. For the purposes of this topic, you don't need to understand how this bonding has come about. \text{Mg}O_{s} \longrightarrow \text{Mg}^{2+}_{(g)} + O^{2-}_{(g)} \\{\Delta}H_{\text{lattice}} = +3889~kJ~mol^{-1} THERMAL STABILITY OF THE GROUP 2 CARBONATES AND NITRATES. The shading is intended to show that there is a greater chance of finding them around the oxygen atoms than near the carbon. 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. The enthalpy changes (in kJ mol-1) which I calculated from enthalpy changes of formation are given in the table. 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