This is an old history: it goes back to C.
There is no null keyword in C. A null pointer constant in C is either:
- an integral constant expression with value 0, like 0,0L,'\0'(remember thatcharis an integral type),(2-4/2)
- such expression cast to void*, like(void*)0,(void*)0L,(void*)'\0',(void*)(2-4/2)
The NULL macro (not a keyword!) expands to such null pointer constant.
In the first C++ design, only the integral constant expression was allowed as a null pointer constant. Recently std::nullptr_t was added to C++.
In C++, but not in C, a const variable of integral type initialized with an integral constant expression is an integral constant expression:
const int c = 3;
int i;
switch(i) {
case c: // valid C++
// but invalid C!
}
So a const char initialized with the expression '\0' is a null pointer constant:
int zero() { return 0; }
void foo() {
    const char k0 = '\0',
               k1 = 1,
               c = zero();
    int *pi;
    pi = k0; // OK (constant expression, value 0)
    pi = k1; // error (value 1)
    pi = c; // error (not a constant expression)
}
And you think this is not sound language design?
Updated to include relevant parts of C99 standard...
According to §6.6.6...
An integer constant expression shall have integer type and shall only have operands
  that are integer constants, enumeration constants, character constants, sizeof
  expressions whose results are integer constants, and floating constants that are the
  immediate operands of casts. Cast operators in an integer constant expression shall only
  convert arithmetic types to integer types, except as part of an operand to the sizeof
  operator.
Some clarifications for C++-only programmers:
- C uses the term "constant" for what C++ programmers know as a "literal".
- In C++, sizeofis always a compile time constant; but C has variable length arrays, sosizeofis sometimes not a compile time constant.
Then, we see §6.3.2.3.3 states...
An integer constant expression with the value 0, or such an expression cast to type
  void *, is called a null pointer constant. If a null pointer constant is converted to a pointer type, the resulting pointer, called a null pointer, is guaranteed to compare unequal to a pointer to any object or function.
To see just how old this functionality is, see the identical mirrored parts in the C99 standard...
§6.6.6
An integer constant expression shall have integer type and shall only have operands that are integer constants, enumeration constants, character constants, sizeof expressions whose results are integer constants, and floating constants that are the immediate operands of casts. Cast operators in an integer constant expression shall only convert arithmetic types to integer types, except as part of an operand to the sizeof operator.
§6.3.2.3.3
An integer constant expression with the value 0, or such an expression cast to type
  void *, is called a null pointer constant. If a null pointer constant is converted to a pointer type, the resulting pointer, called a null pointer, is guaranteed to compare unequal to a pointer to any object or function.