Different physical chemical methods were used to study the thermochemical processes in a system involving a natural phosphate and complex acid salts of ammonium sulphate. The products of decomposition of the double ammonium salt and the products of their interactions with the phosphate were identified. The formation of ammonium and calcium polyphosphates and the disproportionation of P3O105- and P2O74- to PO43- and PO3- were found to depend on the circumstances of the thermal interactions.