Changes in pressure for an equilibrium reaction containing a solid/liquid on one side only

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For a reaction where there is only one solid/liquid present, but gases present as both reactants and products (are there any examples of this type of reaction?):



$$ceA(s) + B(g) <=> C(g),$$



if pressure is increased, it will favour the formation of the side not containing the solid/liquid (e.g. the forward reaction favoured), so as to decrease pressure of system – since one mole of a gas molecules has a considerably lower volume than a mole of any solid or liquid (far more spread out).



And the opposite if pressure decreased.



E.g. all that is considered is which side the solid/liquid is on, not the moles of gas present on either side. Is this true?










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    2












    $begingroup$


    For a reaction where there is only one solid/liquid present, but gases present as both reactants and products (are there any examples of this type of reaction?):



    $$ceA(s) + B(g) <=> C(g),$$



    if pressure is increased, it will favour the formation of the side not containing the solid/liquid (e.g. the forward reaction favoured), so as to decrease pressure of system – since one mole of a gas molecules has a considerably lower volume than a mole of any solid or liquid (far more spread out).



    And the opposite if pressure decreased.



    E.g. all that is considered is which side the solid/liquid is on, not the moles of gas present on either side. Is this true?










    share|improve this question











    $endgroup$














      2












      2








      2





      $begingroup$


      For a reaction where there is only one solid/liquid present, but gases present as both reactants and products (are there any examples of this type of reaction?):



      $$ceA(s) + B(g) <=> C(g),$$



      if pressure is increased, it will favour the formation of the side not containing the solid/liquid (e.g. the forward reaction favoured), so as to decrease pressure of system – since one mole of a gas molecules has a considerably lower volume than a mole of any solid or liquid (far more spread out).



      And the opposite if pressure decreased.



      E.g. all that is considered is which side the solid/liquid is on, not the moles of gas present on either side. Is this true?










      share|improve this question











      $endgroup$




      For a reaction where there is only one solid/liquid present, but gases present as both reactants and products (are there any examples of this type of reaction?):



      $$ceA(s) + B(g) <=> C(g),$$



      if pressure is increased, it will favour the formation of the side not containing the solid/liquid (e.g. the forward reaction favoured), so as to decrease pressure of system – since one mole of a gas molecules has a considerably lower volume than a mole of any solid or liquid (far more spread out).



      And the opposite if pressure decreased.



      E.g. all that is considered is which side the solid/liquid is on, not the moles of gas present on either side. Is this true?







      physical-chemistry equilibrium pressure






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      share|improve this question













      share|improve this question




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      edited Jan 3 at 6:48









      andselisk

      14.4k649107




      14.4k649107










      asked Jan 3 at 6:17









      frog0101frog0101

      141




      141




















          4 Answers
          4






          active

          oldest

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          $begingroup$

          There are many examples of such reactions, for instance:



          $$
          beginalign
          ceS (s) + O2 (g) &<=> SO2 (g)\
          ceC (s) + 2 H2 (g) &<=> CH4 (g)\
          ceNi (s) + 4 CO (g) &<=> Ni(CO)4 (g)
          endalign
          $$



          However, your assumption




          all that is considered is which side the solid/liquid is on, not the moles of gas present on either side




          is not correct. Since shift of equilibrium according to Le Chatelier’s principle depends on partial pressures, which in turn, rely on molar ratio of gaseous reactants and products, decrease/increase of pressure doesn't depend on which side of the reaction solid/liquid participant is located; instead, it is defined for each system individually based on ratio between gaseous products and reactants.






          share|improve this answer











          $endgroup$




















            1












            $begingroup$

            If you want to discuss using Ideal conditions, then pressure should have no effect on that equilibrium - the reaction produces and consumes an exact equal amount of gas - and with ideal conditions individual molecules have zero volume so the solid part doesn't take any. The assumption is fairly good, the volume of a mole of solid is completely negligible compared to a mole of gas of the same compound.



            If you use Real conditions you have to evaluate the compressibility of the gas vs gas+liquid/solid along with some thermodynamic data about the compounds to get the shift of internal energy per atmosphere and compound. The magnitudes of these should show which way the equilibrium goes. And if you are really fond of doing long and complicated integrals and Legendre transforms and whatnot, you could also try to estimate where the new equilibrium would be by finding the minimum of the Helmholtz' free energy with varying the ratio of pressures of C and B but it does not sound like an interesting evening to me.






            share|improve this answer









            $endgroup$




















              0












              $begingroup$

              Well the reaction will favor the side not containing the solid/liquid, this is not true. It will favor the side where number of gaseous moles is less. This will be found giving a balanced chemical reaction.






              share|improve this answer









              $endgroup$




















                0












                $begingroup$

                The equilibrium constant $K_p$ is defined in terms of the free energy of the standard states of the gaseous species at 1 atmosphere pressure so is independent of pressure. This means that if the pressure is changed the degree of dissociation $alpha$ may change and this is determined by working out the equilibrium in terms of $alpha$ and the partial pressures.



                If the partial pressures are expressed as mole fractions $x$ then $K_x =K_pP^-Delta n$ where $Delta n$ is the change in the number of moles, products minus reactants. Thus, unless $Delta n =0 $, which is your case, the mole fractions of the components will vary if the total pressure changes even though $K_p$ does not. If the partial pressures are expressed as concentrations then $K_c=K_P(RT)^-Delta n$ and $K_c$ like $K_p$ is independent of pressure for perfect gasses.






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                  4 Answers
                  4






                  active

                  oldest

                  votes








                  4 Answers
                  4






                  active

                  oldest

                  votes









                  active

                  oldest

                  votes






                  active

                  oldest

                  votes









                  4












                  $begingroup$

                  There are many examples of such reactions, for instance:



                  $$
                  beginalign
                  ceS (s) + O2 (g) &<=> SO2 (g)\
                  ceC (s) + 2 H2 (g) &<=> CH4 (g)\
                  ceNi (s) + 4 CO (g) &<=> Ni(CO)4 (g)
                  endalign
                  $$



                  However, your assumption




                  all that is considered is which side the solid/liquid is on, not the moles of gas present on either side




                  is not correct. Since shift of equilibrium according to Le Chatelier’s principle depends on partial pressures, which in turn, rely on molar ratio of gaseous reactants and products, decrease/increase of pressure doesn't depend on which side of the reaction solid/liquid participant is located; instead, it is defined for each system individually based on ratio between gaseous products and reactants.






                  share|improve this answer











                  $endgroup$

















                    4












                    $begingroup$

                    There are many examples of such reactions, for instance:



                    $$
                    beginalign
                    ceS (s) + O2 (g) &<=> SO2 (g)\
                    ceC (s) + 2 H2 (g) &<=> CH4 (g)\
                    ceNi (s) + 4 CO (g) &<=> Ni(CO)4 (g)
                    endalign
                    $$



                    However, your assumption




                    all that is considered is which side the solid/liquid is on, not the moles of gas present on either side




                    is not correct. Since shift of equilibrium according to Le Chatelier’s principle depends on partial pressures, which in turn, rely on molar ratio of gaseous reactants and products, decrease/increase of pressure doesn't depend on which side of the reaction solid/liquid participant is located; instead, it is defined for each system individually based on ratio between gaseous products and reactants.






                    share|improve this answer











                    $endgroup$















                      4












                      4








                      4





                      $begingroup$

                      There are many examples of such reactions, for instance:



                      $$
                      beginalign
                      ceS (s) + O2 (g) &<=> SO2 (g)\
                      ceC (s) + 2 H2 (g) &<=> CH4 (g)\
                      ceNi (s) + 4 CO (g) &<=> Ni(CO)4 (g)
                      endalign
                      $$



                      However, your assumption




                      all that is considered is which side the solid/liquid is on, not the moles of gas present on either side




                      is not correct. Since shift of equilibrium according to Le Chatelier’s principle depends on partial pressures, which in turn, rely on molar ratio of gaseous reactants and products, decrease/increase of pressure doesn't depend on which side of the reaction solid/liquid participant is located; instead, it is defined for each system individually based on ratio between gaseous products and reactants.






                      share|improve this answer











                      $endgroup$



                      There are many examples of such reactions, for instance:



                      $$
                      beginalign
                      ceS (s) + O2 (g) &<=> SO2 (g)\
                      ceC (s) + 2 H2 (g) &<=> CH4 (g)\
                      ceNi (s) + 4 CO (g) &<=> Ni(CO)4 (g)
                      endalign
                      $$



                      However, your assumption




                      all that is considered is which side the solid/liquid is on, not the moles of gas present on either side




                      is not correct. Since shift of equilibrium according to Le Chatelier’s principle depends on partial pressures, which in turn, rely on molar ratio of gaseous reactants and products, decrease/increase of pressure doesn't depend on which side of the reaction solid/liquid participant is located; instead, it is defined for each system individually based on ratio between gaseous products and reactants.







                      share|improve this answer














                      share|improve this answer



                      share|improve this answer








                      edited Jan 3 at 7:04

























                      answered Jan 3 at 6:43









                      andseliskandselisk

                      14.4k649107




                      14.4k649107





















                          1












                          $begingroup$

                          If you want to discuss using Ideal conditions, then pressure should have no effect on that equilibrium - the reaction produces and consumes an exact equal amount of gas - and with ideal conditions individual molecules have zero volume so the solid part doesn't take any. The assumption is fairly good, the volume of a mole of solid is completely negligible compared to a mole of gas of the same compound.



                          If you use Real conditions you have to evaluate the compressibility of the gas vs gas+liquid/solid along with some thermodynamic data about the compounds to get the shift of internal energy per atmosphere and compound. The magnitudes of these should show which way the equilibrium goes. And if you are really fond of doing long and complicated integrals and Legendre transforms and whatnot, you could also try to estimate where the new equilibrium would be by finding the minimum of the Helmholtz' free energy with varying the ratio of pressures of C and B but it does not sound like an interesting evening to me.






                          share|improve this answer









                          $endgroup$

















                            1












                            $begingroup$

                            If you want to discuss using Ideal conditions, then pressure should have no effect on that equilibrium - the reaction produces and consumes an exact equal amount of gas - and with ideal conditions individual molecules have zero volume so the solid part doesn't take any. The assumption is fairly good, the volume of a mole of solid is completely negligible compared to a mole of gas of the same compound.



                            If you use Real conditions you have to evaluate the compressibility of the gas vs gas+liquid/solid along with some thermodynamic data about the compounds to get the shift of internal energy per atmosphere and compound. The magnitudes of these should show which way the equilibrium goes. And if you are really fond of doing long and complicated integrals and Legendre transforms and whatnot, you could also try to estimate where the new equilibrium would be by finding the minimum of the Helmholtz' free energy with varying the ratio of pressures of C and B but it does not sound like an interesting evening to me.






                            share|improve this answer









                            $endgroup$















                              1












                              1








                              1





                              $begingroup$

                              If you want to discuss using Ideal conditions, then pressure should have no effect on that equilibrium - the reaction produces and consumes an exact equal amount of gas - and with ideal conditions individual molecules have zero volume so the solid part doesn't take any. The assumption is fairly good, the volume of a mole of solid is completely negligible compared to a mole of gas of the same compound.



                              If you use Real conditions you have to evaluate the compressibility of the gas vs gas+liquid/solid along with some thermodynamic data about the compounds to get the shift of internal energy per atmosphere and compound. The magnitudes of these should show which way the equilibrium goes. And if you are really fond of doing long and complicated integrals and Legendre transforms and whatnot, you could also try to estimate where the new equilibrium would be by finding the minimum of the Helmholtz' free energy with varying the ratio of pressures of C and B but it does not sound like an interesting evening to me.






                              share|improve this answer









                              $endgroup$



                              If you want to discuss using Ideal conditions, then pressure should have no effect on that equilibrium - the reaction produces and consumes an exact equal amount of gas - and with ideal conditions individual molecules have zero volume so the solid part doesn't take any. The assumption is fairly good, the volume of a mole of solid is completely negligible compared to a mole of gas of the same compound.



                              If you use Real conditions you have to evaluate the compressibility of the gas vs gas+liquid/solid along with some thermodynamic data about the compounds to get the shift of internal energy per atmosphere and compound. The magnitudes of these should show which way the equilibrium goes. And if you are really fond of doing long and complicated integrals and Legendre transforms and whatnot, you could also try to estimate where the new equilibrium would be by finding the minimum of the Helmholtz' free energy with varying the ratio of pressures of C and B but it does not sound like an interesting evening to me.







                              share|improve this answer












                              share|improve this answer



                              share|improve this answer










                              answered Jan 3 at 10:00









                              Stian YttervikStian Yttervik

                              2,144413




                              2,144413





















                                  0












                                  $begingroup$

                                  Well the reaction will favor the side not containing the solid/liquid, this is not true. It will favor the side where number of gaseous moles is less. This will be found giving a balanced chemical reaction.






                                  share|improve this answer









                                  $endgroup$

















                                    0












                                    $begingroup$

                                    Well the reaction will favor the side not containing the solid/liquid, this is not true. It will favor the side where number of gaseous moles is less. This will be found giving a balanced chemical reaction.






                                    share|improve this answer









                                    $endgroup$















                                      0












                                      0








                                      0





                                      $begingroup$

                                      Well the reaction will favor the side not containing the solid/liquid, this is not true. It will favor the side where number of gaseous moles is less. This will be found giving a balanced chemical reaction.






                                      share|improve this answer









                                      $endgroup$



                                      Well the reaction will favor the side not containing the solid/liquid, this is not true. It will favor the side where number of gaseous moles is less. This will be found giving a balanced chemical reaction.







                                      share|improve this answer












                                      share|improve this answer



                                      share|improve this answer










                                      answered Jan 3 at 6:39









                                      harshit54harshit54

                                      1068




                                      1068





















                                          0












                                          $begingroup$

                                          The equilibrium constant $K_p$ is defined in terms of the free energy of the standard states of the gaseous species at 1 atmosphere pressure so is independent of pressure. This means that if the pressure is changed the degree of dissociation $alpha$ may change and this is determined by working out the equilibrium in terms of $alpha$ and the partial pressures.



                                          If the partial pressures are expressed as mole fractions $x$ then $K_x =K_pP^-Delta n$ where $Delta n$ is the change in the number of moles, products minus reactants. Thus, unless $Delta n =0 $, which is your case, the mole fractions of the components will vary if the total pressure changes even though $K_p$ does not. If the partial pressures are expressed as concentrations then $K_c=K_P(RT)^-Delta n$ and $K_c$ like $K_p$ is independent of pressure for perfect gasses.






                                          share|improve this answer









                                          $endgroup$

















                                            0












                                            $begingroup$

                                            The equilibrium constant $K_p$ is defined in terms of the free energy of the standard states of the gaseous species at 1 atmosphere pressure so is independent of pressure. This means that if the pressure is changed the degree of dissociation $alpha$ may change and this is determined by working out the equilibrium in terms of $alpha$ and the partial pressures.



                                            If the partial pressures are expressed as mole fractions $x$ then $K_x =K_pP^-Delta n$ where $Delta n$ is the change in the number of moles, products minus reactants. Thus, unless $Delta n =0 $, which is your case, the mole fractions of the components will vary if the total pressure changes even though $K_p$ does not. If the partial pressures are expressed as concentrations then $K_c=K_P(RT)^-Delta n$ and $K_c$ like $K_p$ is independent of pressure for perfect gasses.






                                            share|improve this answer









                                            $endgroup$















                                              0












                                              0








                                              0





                                              $begingroup$

                                              The equilibrium constant $K_p$ is defined in terms of the free energy of the standard states of the gaseous species at 1 atmosphere pressure so is independent of pressure. This means that if the pressure is changed the degree of dissociation $alpha$ may change and this is determined by working out the equilibrium in terms of $alpha$ and the partial pressures.



                                              If the partial pressures are expressed as mole fractions $x$ then $K_x =K_pP^-Delta n$ where $Delta n$ is the change in the number of moles, products minus reactants. Thus, unless $Delta n =0 $, which is your case, the mole fractions of the components will vary if the total pressure changes even though $K_p$ does not. If the partial pressures are expressed as concentrations then $K_c=K_P(RT)^-Delta n$ and $K_c$ like $K_p$ is independent of pressure for perfect gasses.






                                              share|improve this answer









                                              $endgroup$



                                              The equilibrium constant $K_p$ is defined in terms of the free energy of the standard states of the gaseous species at 1 atmosphere pressure so is independent of pressure. This means that if the pressure is changed the degree of dissociation $alpha$ may change and this is determined by working out the equilibrium in terms of $alpha$ and the partial pressures.



                                              If the partial pressures are expressed as mole fractions $x$ then $K_x =K_pP^-Delta n$ where $Delta n$ is the change in the number of moles, products minus reactants. Thus, unless $Delta n =0 $, which is your case, the mole fractions of the components will vary if the total pressure changes even though $K_p$ does not. If the partial pressures are expressed as concentrations then $K_c=K_P(RT)^-Delta n$ and $K_c$ like $K_p$ is independent of pressure for perfect gasses.







                                              share|improve this answer












                                              share|improve this answer



                                              share|improve this answer










                                              answered Jan 3 at 12:58









                                              porphyrinporphyrin

                                              17.1k2852




                                              17.1k2852



























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