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Let \\(f \\colon \\mathbb R^{d} \\rightarrow \\mathbb R\\) be a Lipschitz function, \\(u \\in W^{1,1}_{ \\text{loc}} (\\mathbb R^{N}; \\mathbb R^{d})\\) and let \\(\\{e_{1} , \\dots , e_{d} \\}\\) be a (not necessarily orthonormal) basis in \\( \\mathbb R^{d}\\). We say that the classical chain rule holds for \\(f\\) and \\(u\\) with respect to the coordinate system \\(\\{e_{1} , \\dots , e_{d} \\}\\) if for every \\(i =1, \\dots, d\\), \\(\\partial f / \\partial e_{i}\\) exists at \\(u(x)\\) for \\(\\mathcal L ^{N}\\) -a.e.\\ \\(x\\) in the set where some \\( \\partial u_{i} /\\partial x_{j}\\) does not vanish, and for such \\(x\\),  \\[ \\frac{\\partial}{\\partial x_{j}}(f \\circ u)(x) = \\sum_{i=1}^{d} \\frac{\\partial f}{ \\partial e_{i}} (u(x))\\frac{\\partial u_{i}}{\\partial x_{j}}(x)~(j=1,\\dots,N), \\]  where \\(\\frac{\\partial f}{ \\partial e_{i}} (u(x))\\frac{\\partial u_{i}}{\\partial x_{j}}(x)\\) is interpreted to be zero whenever \\(\\frac{\\partial u_{i}}{\\partial x_{j}}(x)=0\\). Set  \\[ \\Sigma^{f} = \\{x \\in \\mathbb R^{d} \\colon f \\text{ is not differentiable at }x\\}. \\]  For an \\( {\\mathcal H}^{k}\\)-rectifiable set \\(E \\subseteq \\mathbb R^{d}\\) the approximate tangent space of \\(E\\) at \\(x \\in E\\) is denoted by \\(\\text{Tan}^{k} (E, x)\\). We use  \\[ I (k, d ) = \\{\\alpha = (\\alpha_{1} , \\dots , \\alpha_{k} ) \\in \\mathbb N ^{k} \\colon 1 \\leq \\alpha_{1} < \\dots < \\alpha_{k} \\leq d \\}. \\]  Finally, \\(\\mathcal A _{k} (\\mathbb R^{N}; \\mathbb R^{d})\\) stands for those functions \\(u \\in W^{1,1}_{ \\text{loc}} (\\mathbb R^{N}; \\mathbb R^{d})\\) for which \\(\\text{rank}(\\nabla u(x))\\) is either zero or greater than or equal to \\(k\\) for \\(\\mathcal L ^{N}\\)-a.e.\\ \\(x \\in \\mathbb R ^{N}\\). The first main result of the paper is the following.  Theorem. Let \\(f \\colon \\mathbb R^{d} \\rightarrow \\mathbb R\\) be a Lipschitz function, let \\(\\{e_{1} , \\dots , e_{d} \\}\\) be a basis in \\(\\mathbb R^{d}\\), and let \\(1 \\leq k \\leq \\min\\{N , d \\}\\). Assume that for every \\({\\mathcal H}^{k}\\)-rectifiable set \\(E \\subseteq \\Sigma^{f}\\) and for \\( {\\mathcal H}^{k}\\)-a.e.\\ \\(x \\in E\\) there exists \\(\\alpha \\in I (k, d )\\) depending on \\(x\\) such that  \\[ \\text{Tan}^{k} (E, x) = \\text{span}\\{e_{\\alpha_{1}} , \\dots , e_{\\alpha_{ k}} \\}. \\leqno (1) \\]  Then the classical chain rule holds for \\(f\\) and \\(u \\in \\mathcal A _{k} (\\mathbb R^{N}; \\mathbb R^{d})\\) with respect to the coordinate system \\(\\{e_{1} , \\dots , e_{d} \\}\\). Moreover, if \\( k = d-1\\), then (1) is also necessary for the validity of the classical chain rule for \\(u \\in \\mathcal A _{d -1} (\\mathbb R^{N}; \\mathbb R^{d})\\).  Observe that the special \\(d=2\\), \\(k=1\\) case of the above theorem is a necessary and sufficient condition for the classical chain rule in the class \\(W^{1,1}_{ \\text{loc}} (\\mathbb R^{N}; \\mathbb R^{2})\\) for a fixed coordinate system. The authors show that if \\(d \\geq 3\\) then for any orthonormal basis \\(\\{e_{1} , \\dots , e_{d} \\}\\) and any \\(\\mathcal H ^{d-2}\\)-rectifiable Borel set \\(E \\subseteq \\mathbb R^{d}\\) there exists a Lipschitz function \\(f \\colon \\mathbb R^{d} \\rightarrow \\mathbb R\\) such that \\(\\Sigma^{f} \\subseteq E\\), \\(\\mathcal H ^{d-2} (E \\setminus \\Sigma^{f})=0\\) and the classical chain rule holds for \\(f\\) and \\(u \\in W^{1,1}_{ \\text{loc}} (\\mathbb R^{N}; \\mathbb R^{d})\\) for any \\(N \\in \\mathbb N\\) with respect to the coordinate system \\(\\{e_{1} , \\dots , e_{d} \\}\\). That is the condition of the theorem above is not necessary for \\(d \\geq 3\\) and \\(k \\leq d-2\\). On the other hand, the second main result of the paper characterizes when the classical chain rule holds with respect to every coordinate system.  Theorem. Let \\(f \\colon \\mathbb R^{d} \\rightarrow \\mathbb R\\) be a Lipschitz function. Then the classical chain rule holds for \\(f\\) and for every \\(u \\in W^{1,1}_{ \\text{loc}} (\\mathbb R^{N}; \\mathbb R^{d})\\) with respect to every coordinate system in \\(\\mathbb R^{d}\\) if and only if \\(\\Sigma^{f}\\) is purely \\(\\mathcal H ^{1}\\)-unrectifiable.  The sufficiency part of this result is due to M.\\ Marcus and V.\\ J.\\ Mizel. The authors also obtain the analogues of the theorems above for the classical chain rule involving \\(u \\in BV_{ \\text{loc}} (\\mathbb R^{N}; \\mathbb R^{d})\\). The proof of the results relies on a new characterization of the pure \\(\\mathcal H^{k}\\)-unrectifiability of \\(\\Sigma^{f}\\) for Lipschitz functions 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