The group of machine language instructions that a computer can follow, which may range from a handful to several hundred. It is a fundamental architectural component of a CPU and is either built into the CPU or into microcode, a layer between the instruction set and the circuitry. The instruction length is generally from one to four bytes long. See CISC, RISC, machine language, microcode and CPU.
Machine code - simple instructions that are executed directly by the CPU
As we should hopefully already know, computers are calculators that can only count from 0 to 1.
We have to give them instructions, so they know what to do.
Machine code allows computers to perform the most basic, but essential tasks. Amongst others, the following instructions are important for all processors:
LDA - Loads the contents of the memory address or integer into the accumulator
ADD - Adds the contents of the memory address or integer to the accumulator
STO - Stores the contents of the accumulator into the addressed location
Assembly code is the easy to read interpretation of machine code, there is a one to one matching, one line of assembly equals one line of machine code:
Instruction set - the range of instructions that a CPU can execute
There are many different instructions that we can use in machine code, you have already met three (LDA, ADD, STO), but some processors will be capable of understanding many more. The selection of instructions that a machine can understand is called the instruction set.
Apart from some simple instructions common to all processors, instructions differ CPU to CPU, depending on the CPU's purpose and complexity. So yes, there are some different instructions between 64 and 86 bit architecture
you might also try:
https://en.wikipedia.org/wiki/Instruction_set
http://en.wikibooks.org/wiki/A-level_Computing/AQA/Computer_Components,_The_Stored_Program_Concept_and_the_Internet/Machine_Level_Architecture/Machine_code_and_processor_instruction_set